Synergistic pesticidal compositions and related methods

ABSTRACT

A pesticidal composition comprises a synergistically effective amount of a pyrethroid-based or pyrethrin-based sodium channel modulator compound and a pesticide selected from N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide (I), N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl) propanamide (II), or any agriculturally acceptable salt thereof. A method of controlling pests comprises applying the pesticidal composition near a population of pests. A method of protecting a plant from infestation and attack by insects comprises contacting the plant with the synergistic pesticidal composition.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional PatentApplication Ser. No. 61/894,128, filed Oct. 22, 2013, the disclosure ofwhich is hereby incorporated herein in its entirety by this reference.

TECHNICAL FIELD

This disclosure relates to the field of compounds having pesticidalutility against pests in Phyla Nematoda, Arthropoda, and/or Mollusca,processes to produce such compounds and intermediates used in suchprocesses. These compounds may be used, for example, as nematicides,acaricides, miticides, and/or molluscicides.

BACKGROUND

Controlling pest populations is essential to human health, modernagriculture, food storage, and hygiene. There are more than ten thousandspecies of pests that cause losses in agriculture and the world-wideagricultural losses amount to billions of U.S. dollars each year.Accordingly, there exists a continuous need for new pesticides and formethods of producing and using such pesticides.

The Insecticide Resistance Action Committee (IRAC) has classifiedinsecticides into categories based on the best available evidence of themode of action of such insecticides. Insecticides in the IRAC Mode ofAction Group 3A are sodium channel modulators that are pyrethroid-basedor pyrethrin-based compounds. The insecticides in this class arebelieved to keep sodium channels open, causing hyperexcitation and, insome cases, nerve block in the affected insects. Sodium channels areinvolved in the propagation of action potentials along nerve axons.Examples of insecticides in the IRAC Mode of Action Group 3A class arelambda-cyhalothrin, acrinathrin, allethrin, d-cis-trans allethrin,d-trans allethrin, bifenthrin, bioallethrin, bioallethrin,S-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin,beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, cypermethrin,alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin,zeta-cypermethrin, cyphenothrin [(1R)-trans-isomers], deltamethrin,empenthrin [(EZ)-(1R)-isomers], esfenvalerate, etofenprox,fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate,halfenprox, imiprothrin, kadethrin, permethrin, phenothrin[(1R)-trans-isomer], prallethrin, pyrethrins (pyrethrum), resmethrin,silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R)-isomers],tralomethrin, and transfluthrin.

Lambda-cyhalothrin,3-(2-chloro-3,3,3-trifluoro-1-propenyl)-2,2-dimethyl-cyano-(3-phenoxyphenyl)methylcyclopropanecarboxylate, belongs to a group of chemicals calledsynthetic pyrethroids. Synthetic pyrethroids are manmade insecticidesthat mimic the structure and insecticidal properties of thenaturally-occurring insecticide pyrethrum, which comes from the crushedpetals of the Chrysanthemum flower.

Although the rotational application of pesticides having different modesof action may be adopted for good pest management practice, thisapproach does not necessarily give satisfactory pest control.Furthermore, even though combinations of pesticides have been studied, ahigh synergistic action has not always been found.

DETAILED DESCRIPTION

As used herein, the term “synergistic effect” or grammatical variationsthereof means and includes a cooperative action encountered in acombination of two or more active compounds in which the combinedactivity of the two or more active compounds exceeds the sum of theactivity of each active compound alone.

The term “synergistically effective amount,” as used herein, means andincludes an amount of two or more active compounds that provides asynergistic effect defined above.

The term “pesticidally effective amount,” as used herein, means andincludes an amount of active pesticide that causes an adverse effect tothe at least one pest, wherein the adverse effect may include deviationsfrom natural development, killing, regulation, or the like.

As used herein, the term “control” or grammatical variations thereofmeans and includes regulating the number of living pests or regulatingthe number of viable eggs of the pests or both.

The term “pyrethroid-based or pyrethrin-based sodium channel modulatorcompound,” as used herein, means and includes any insecticides that areclassified by the Insecticide Resistance Action Committee (IRAC), basedon the best available evidence of the mode of action, to be within theIRAC Mode of Action Group 3A.

In one particular embodiment, a pesticidal composition comprises asynergistically effective amount of a pyrethroid-based orpyrethrin-based sodium channel modulator compound in combination with apesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.

It is appreciated that a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide (I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof may be oxidized tothe corresponding sulfone in the presence of oxygen.

As shown in the examples, the existence of synergistic effect isdetermined using the method described in Colby S. R., “CalculatingSynergistic and Antagonistic Responses of Herbicide Combinations,”Weeds, 1967, 15, 20-22.

Surprisingly, it has been found that the pesticidal composition of thepresent disclosure has superior pest control at lower levels of thecombined concentrations of the pyrethroid-based or pyrethrin-basedsodium channel modulator compound and the pesticide (I), (II), or anyagriculturally acceptable salt thereof employed than that which may beachieved when the pyrethroid-based or pyrethrin-based sodium channelmodulator compound and the pesticide (I), (II), or any agriculturallyacceptable salt thereof are applied alone. In other words, thesynergistic pesticidal composition is not a mere admixture of two activecompounds resulting in the aggregation of the properties of the activecompounds employed in the composition.

In some embodiments, the pesticidal compositions may comprise asynergistically effective amount of a pesticide selected from (I), (II),or any agriculturally acceptable salt thereof in combination with atleast one of lambda-cyhalothrin, acrinathrin, allethrin, d-cis-transallethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrinS-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin,beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, cypermethrin,alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin,zeta-cypermethrin, cyphenothrin [(1R)-trans-isomers], deltamethrin,empenthrin [(EZ)-(1R)-isomers], esfenvalerate, etofenprox,fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate,halfenprox, imiprothrin, kadethrin, permethrin, phenothrin[(1R)-trans-isomer], prallethrin, pyrethrins (pyrethrum), resmethrin,silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R)-isomers],tralomethrin, and transfluthrin.

In other embodiments, the pesticidal compositions may comprise asynergistically effective amount of lambda-cyhalothrin combination witha pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.

Table 1A shows weight ratios of the pesticide (I), (II), or anyagriculturally acceptable salt thereof to the pyrethroid-based orpyrethrin-based sodium channel modulator compound in the synergisticpesticidal compositions. In some embodiments, the weight ratio of thepesticide to the pyrethroid-based or pyrethrin-based sodium channelmodulator compound may be between about 20:1 and about 1:20. In someembodiments, the weight ratio of the pesticide to the pyrethroid-basedor pyrethrin-based sodium channel modulator compound may be betweenabout 15:1 and about 1:15. In some embodiments, the weight ratio of thepesticide to the pyrethroid-based or pyrethrin-based sodium channelmodulator compound may be between about 10:1 and about 1:10. In someembodiments, the weight ratio of the pesticide to the pyrethroid-basedor pyrethrin-based sodium channel modulator compound may be betweenabout 5:1 and about 1:5. In some embodiments, the weight ratio of thepesticide to the pyrethroid-based or pyrethrin-based sodium channelmodulator compound may be between about 4:1 and about 1:4. In someembodiments, the weight ratio of the pesticide to the pyrethroid-basedor pyrethrin-based sodium channel modulator compound may be betweenabout 3:1 and about 1:3. In some embodiments, the weight ratio of thepesticide to the pyrethroid-based or pyrethrin-based sodium channelmodulator compound may be between about 2:1 and about 1:2. In someembodiments, the weight ratio of the pesticide to the pyrethroid-basedor pyrethrin-based sodium channel modulator compound may be about 1:1.Additionally, the weight ratio limits of the pesticide to thepyrethroid-based or pyrethrin-based sodium channel modulator compound inthe aforementioned embodiments may be interchangeable. By way ofnon-limiting example, the weight ratio of the pesticide selected from(I), (II), or any agriculturally acceptable salt thereof to thepyrethroid-based or pyrethrin-based sodium channel modulator compoundmay be between about 1:3 and about 20:1.

TABLE 1A Range of the Weight Ratio of Pesticide I or II toPyrethroid-based or Pyrethrin- No. based Sodium Channel ModulatorCompound 1 20:1 to 1:20 2 15:1 to 1:15 3 10:1 to 1:10 4 5:1 to 1:5 5 4:1to 1:4 6 3:1 to 1:3 7 2:1 to 1:2 8 1:1

Weight ratios of the pesticide (I), (II), or any agriculturallyacceptable salt thereof to the pyrethroid-based or pyrethrin-basedsodium channel modulator compound envisioned to be synergisticpesticidal compositions may be depicted as X:Y; wherein X is the partsby weight of the pesticide (I), (II), or any agriculturally acceptablesalt thereof, and Y is the parts by weight of the pyrethroid-based orpyrethrin-based sodium channel modulator compound. The numerical rangeof the parts by weight for X is 0<X≦20 and the parts by weight for Y is0<Y≦20 as shown graphically in table 1B. By way of non-limiting example,the weight ratio of the pesticide to the pyrethroid-based orpyrethrin-based sodium channel modulator compound may be about 20:1.

TABLE 1B Pyrethroid-based or pyrethrin-based 20 X, Y X, Y sodium channelmodulator 15 X, Y X, Y X, Y compound (Y) Parts by weight 10 X, Y X, Y 5X, Y X, Y X, Y X, Y 4 X, Y X, Y X, Y X, Y 3 X, Y X, Y X, Y X, Y X, Y X,Y 2 X, Y X, Y X, Y X, Y 1 X, Y X, Y X, Y X, Y X, Y X, Y X, Y X, Y 1 2 34 5 10 15 20 Pesticide (I or II) (X) Parts by weight

Ranges of weight ratios of the pesticide (I), (II), or anyagriculturally acceptable salt thereof to the pyrethroid-based orpyrethrin-based sodium channel modulator compound envisioned to besynergistic pesticidal compositions may be depicted as X₁:Y₁ to X₂:Y₂,wherein X and Y are defined as above. In one particular embodiment, therange of weight ratios may be X₁:Y₁ to X₂:Y₂, wherein X₁>Y₁ and X₂<Y₂.By way of non-limiting example, the range of weight ratios of thepesticide to the pyrethroid-based or pyrethrin-based sodium channelmodulator compound may be between about 3:1 and about 1:3. In someembodiments, the range of weight ratios may be X₁:Y₁ to X₂:Y₂, whereinX₁>Y₁ and X₂>Y₂. By way of non-limiting example, the range of weightratios of the pesticide to the pyrethroid-based or pyrethrin-basedsodium channel modulator compound may be between about 15:1 and about3:1. In further embodiments, the range of weight ratios may be X₁:Y₁ toX₂:Y₂, wherein X₁<Y₁ and X₂<Y₂. By way of non-limiting example, therange of weight ratios of the pesticide to the pyrethroid-based orpyrethrin-based sodium channel modulator compound may be between about1:3 and about 1:20.

Table 1C shows further weight ratios of the pesticide (I), (II), or anyagriculturally acceptable salt thereof to the pyrethroid-based orpyrethrin-based sodium channel modulator compound in the synergisticpesticidal compositions, according to particular embodiments of thepresent disclosure.

TABLE 1C Dose Rate of Weight Ratio of Dose Rate Of Pyrethroid-basedPesticide (I or II) to Pesticide or Pyrethrin-based SodiumPyrethroid-based (I or II) Channel Modulator or Pyrethrin-based (weight%) (weight %) Sodium Channel Modulator 0.04 0.00002 ≦2000:1   0.040.000078 ≦513:1  0.04 0.000156 ≦256:1  0.04 0.0003125 ≦128:1  0.040.00125 ≦32:1  0.04 0.0025 ≦16:1  0.04 0.0050 ≦8:1 0.20 0.027 ≦7.5:1  0.13 0.027 ≦5:1 0.0667 0.0167 ≦4:1 0.10 0.027 ≦3.8:1   0.0459 0.0122≦3.8:1   0.0306 0.0122 ≦2.5:1   0.04 0.02 ≦2:1 0.0333 0.0167 ≦2:1 0.03060.0183 ≦1.7:1   0.0333 0.0333 ≦1:1 0.0167 0.0167 ≦1:1 0.0167 0.0333 ≦1:20.002 0.0050   ≦1:2.5

In some particular embodiments, the weight ratio of the pesticide (I),(II), or any agriculturally acceptable salt thereof to thepyrethroid-based or pyrethrin-based sodium channel modulator compoundmay be no more than about 2000:1. In further embodiments, the weightratio of the pesticide to the pyrethroid-based or pyrethrin-based sodiumchannel modulator compound may be no more than about 513:1. In furtherembodiments, the weight ratio of the pesticide to the pyrethroid-basedor pyrethrin-based sodium channel modulator compound may be no more thanabout 256:1. In further embodiments, the weight ratio of the pesticideto the pyrethroid-based or pyrethrin-based sodium channel modulatorcompound may be no more than about 128:1. In further embodiments, theweight ratio of the pesticide to the pyrethroid-based or pyrethrin-basedsodium channel modulator compound may be no more than about 32:1. Infurther embodiments, the weight ratio of the pesticide to thepyrethroid-based or pyrethrin-based sodium channel modulator compoundmay be no more than about 16:1. In further embodiments, the weight ratioof the pesticide to the pyrethroid-based or pyrethrin-based sodiumchannel modulator compound may be no more than about 8:1. In furtherembodiments, the weight ratio of the pesticide to the pyrethroid-basedor pyrethrin-based sodium channel modulator compound may be no more thanabout 7.5:1. In further embodiments, the weight ratio of the pesticideto the pyrethroid-based or pyrethrin-based sodium channel modulatorcompound may be no more than about 5:1. In further embodiments, theweight ratio of the pesticide to the pyrethroid-based or pyrethrin-basedsodium channel modulator compound may be no more than about 4:1. Infurther embodiments, the weight ratio of the pesticide to thepyrethroid-based or pyrethrin-based sodium channel modulator compoundmay be no more than about 3.8:1. In further embodiments, the weightratio of the pesticide to the pyrethroid-based or pyrethrin-based sodiumchannel modulator compound may be no more than about 2.5:1. In furtherembodiments, the weight ratio of the pesticide to the pyrethroid-basedor pyrethrin-based sodium channel modulator compound may be no more thanabout 2:1. In further embodiments, the weight ratio of the pesticide tothe pyrethroid-based or pyrethrin-based sodium channel modulatorcompound may be no more than about 1.7:1. In further embodiments, theweight ratio of the pesticide to the pyrethroid-based or pyrethrin-basedsodium channel modulator compound may be no more than about 1:1. Infurther embodiments, the weight ratio of the pesticide to thepyrethroid-based or pyrethrin-based sodium channel modulator compoundmay be no more than about 1:2. In yet further embodiments, the weightratio of the pesticide to the pyrethroid-based or pyrethrin-based sodiumchannel modulator compound may be no more than about 1:2.5.

The weight ratio of the pesticide (I), (II), or any agriculturallyacceptable salt thereof to the pyrethroid-based or pyrethrin-basedsodium channel modulator compound in the synergistic pesticidalcomposition may be varied and different from those described in table1A, table 1B, and table 1C. One skilled in the art recognizes that thesynergistic effective amount of the combination of active compounds mayvary accordingly to various prevailing conditions. Non-limiting examplesof such prevailing conditions may include the type of pests, the type ofcrops, the mode of application, the application timing, the weatherconditions, the soil conditions, the topographical character, or thelike. It is understood that one skilled in the art may readily determinethe synergistic effective amount of the pyrethroid-based orpyrethrin-based sodium channel modulator compound and the pesticide (I),(II), or any agriculturally acceptable salt thereof accordingly to theprevailing conditions.

In some embodiments, the pesticidal composition may comprise asynergistically effective amount of a pyrethroid-based orpyrethrin-based sodium channel modulator compound in combination with apesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof, and aphytologically-acceptable inert carrier (e.g., solid carrier, or liquidcarrier).

In further embodiments, the pesticidal composition may further compriseat least one additive selected from a surfactant, a stabilizer, anemetic agent, a disintegrating agent, an antifoaming agent, a wettingagent, a dispersing agent, a binding agent, dye, filler, or combinationsthereof.

In particular embodiments, each of the active compounds (apyrethroid-based or pyrethrin-based sodium channel modulator compound,and a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof) may be formulatedseparately as a wettable powder, emulsifiable concentrate, aqueous orliquid flowable, suspension concentrate or any one of the conventionalformulations used for pesticides, and then tank-mixed in the field withwater or other liquid for application as a liquid spray mixture. Whendesired, the separately formulated pesticides may also be appliedsequentially.

In some embodiments, the synergistic pesticidal composition may beformulated into a more concentrated primary composition, which is thendiluted with water or other diluent before use. In such embodiments, thesynergistic pesticidal composition may further comprise a surface activeagent.

In one particular embodiment, the method of protecting a plant frominfestation and attack by insects comprises contacting the plant with apesticidal composition comprising a synergistically effective amount ofa pyrethroid-based or pyrethrin-based sodium channel modulator compound,and a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.

In some embodiments, the pesticidal compositions may be in the form ofsolid. Non-limiting examples of the solid forms may include power, dustor granular formulations.

In other embodiments, the pesticidal compositions may be in the form ofliquid formulation. Examples of the liquid forms may include, but notlimited to, dispersion, suspension, emulsion or solution in appropriateliquid carrier. In particular embodiments, the synergistic pesticidalcompositions may be in the form of liquid dispersion, wherein thesynergistic pesticidal compositions may be dispersed in water or otheragriculturally suitable liquid carrier.

In certain embodiments, the synergistic pesticidal compositions may bein the form of solution in an appropriate organic solvent. In oneembodiment, the spray oils, which are widely used in agriculturalchemistry, may be used as the organic solvent for the synergisticpesticidal compositions.

In one particular embodiment, the method of controlling pests comprisesapplying a pesticidal composition near a population of pests, whereinthe pesticidal composition comprises a synergistically effective amountof a pyrethroid-based or pyrethrin-based sodium channel modulatorcompound in combination with a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.

In some embodiments, the method of controlling pests comprises applyinga pesticidal composition near a population of pests, wherein thepesticidal composition comprises a synergistically effective amount ofthe pesticide selected from (I), (II), or any agriculturally acceptablesalt thereof in combination with at least one of lambda-cyhalothrin,acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin,bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer,bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin,theta-cypermethrin, zeta-cypermethrin, cyphenothrin[(1R)-trans-isomers], deltamethrin, empenthrin [(EZ)-(1R)-isomers],esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate,flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadethrin,permethrin, phenothrin [(1R)-trans-isomer], prallethrin, pyrethrins(pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin,tetramethrin [(1R)-isomers], tralomethrin, and transfluthrin.

In other embodiments, the method of controlling pests comprises applyinga pesticidal composition near a population of pests, wherein thepesticidal composition comprises a synergistically effective amount oflambda-cyhalothrin in combination with a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide (I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide (II), or any agriculturally acceptable saltthereof.

The control of pests may be achieved by applying a pesticidallyeffective amount of the synergistic pesticidal compositions in form ofsprays, topical treatment, gels, seed coatings, microcapsulations,systemic uptake, baits, eartags, boluses, foggers, fumigants aerosols,dusts, or the like.

These disclosed pesticidal compositions may be used, for example, asnematicides, acaricides, miticides, and/or molluscicides.

The pesticidal composition of the present disclosure may be used tocontrol a wide variety of insects. As a non-limiting example, in one ormore embodiments, the pesticidal composition may be used to control oneor more members of at least one of Phylum Arthropoda, Phylum Nematoda,Subphylum Chelicerata, Subphylum Myriapoda, Subphylum Hexapoda, ClassInsecta, Class Arachnida, and Class Symphyla. In at least someembodiments, the method of the present disclosure may be used to controlone or more members of at least one of Class Insecta and ClassArachnida.

As a non-limiting example, in one or more embodiments, the method of thepresent disclosure may be used to control one or more members of atleast one of Phylum Arthropoda, Phylum Nematoda, Subphylum Chelicerata,Subphylum Myriapoda, Subphylum Hexapoda, Class Insecta, Class Arachnida,and Class Symphyla. In at least some embodiments, the method of thepresent disclosure may be used to control one or more members of atleast one of Class Insecta and Class Arachnida.

In additional embodiments, the method of the present disclosure may beused to control members of the Order Coleoptera (beetles) including, butnot limited to, Acanthoscelides spp. (weevils), Acanthoscelides obtectus(common bean weevil), Agrilus planipennis (emerald ash borer), Agriotesspp. (wireworms), Anoplophora glabripennis (Asian longhorned beetle),Anthonomus spp. (weevils), Anthonomus grandis (boll weevil), Aphidiusspp., Apion spp. (weevils), Apogonia spp. (grubs), Ataenius spretulus(Black Turfgrass Ataenius), Atomaria linearis (pygmy mangold beetle),Aulacophore spp., Bothynoderes punctiventris (beet root weevil), Bruchusspp. (weevils), Bruchus pisorum (pea weevil), Cacoesia spp.,Callosobruchus maculatus (southern cow pea weevil), Carpophilushemipteras (dried fruit beetle), Cassida vittata, Cerosterna spp.,Cerotoma spp. (chrysomelids), Cerotoma trifurcata (bean leaf beetle),Ceutorhynchus spp. (weevils), Ceutorhynchus assimilis (cabbage seedpodweevil), Ceutorhynchus napi (cabbage curculio), Chaetocnema spp.(chrysomelids), Colaspis spp. (soil beetles), Conoderus scalaris,Conoderus stigmosus, Conotrachelus nenuphar (plum curculio), Cotinusnitidis (Green June beetle), Crioceris asparagi (asparagus beetle),Cryptolestes ferrugineus (rusty grain beetle), Cryptolestes pusillus(flat grain beetle), Cryptolestes turcicus (Turkish grain beetle),Ctenicera spp. (wireworms), Curculio spp. (weevils), Cyclocephala spp.(grubs), Cylindrocpturus adspersus (sunflower stem weevil), Deporausmarginatus (mango leaf-cutting weevil), Dermestes lardarius (larderbeetle), Dermestes maculates (hide beetle), Diabrotica spp.(chrysomelids), Epilachna varivestis (Mexican bean beetle), Faustinuscubae, Hylobius pales (pales weevil), Hypera spp. (weevils), Hyperapostica (alfalfa weevil), Hyperdoes spp. (Hyperodes weevil),Hypothenemus hampei (coffee berry beetle), Ips spp. (engravers),Lasioderma serricorne (cigarette beetle), Leptinotarsa decemlineata(Colorado potato beetle), Liogenys fuscus, Liogenys suturalis,Lissorhoptrus oryzophilus (rice water weevil), Lyctus spp. (woodbeetles/powder post beetles), Maecolaspis joliveti, Megascelis spp.,Melanotus communis, Meligethes spp., Meligethes aeneus (blossom beetle),Melolontha melolontha (common European cockchafer), Oberea brevis,Oberea linearis, Oryctes rhinoceros (date palm beetle), Oryzaephilusmercator (merchant grain beetle), Oryzaephilus surinamensis (sawtoothedgrain beetle), Otiorhynchus spp. (weevils), Oulema melanopus (cerealleaf beetle), Oulema oryzae, Pantomorus spp. (weevils), Phyllophaga spp.(May/June beetle), Phyllophaga cuyabana (chrysomelids), Phynchites spp.,Popillia japonica (Japanese beetle), Prostephanus truncates (largergrain borer), Rhizopertha dominica (lesser grain borer), Rhizotrogusspp. (European chafer), Rhynchophorus spp. (weevils), Scolytus spp.(wood beetles), Shenophorus spp. (Billbug), Sitona lineatus (pea leafweevil), Sitophilus spp. (grain weevils), Sitophilus granaries (granaryweevil), Sitophilus oryzae (rice weevil), Stegobium paniceum (drugstorebeetle), Tribolium spp. (flour beetles), Tribolium castaneum (red flourbeetle), Tribolium confusum (confused flour beetle), Trogodermavariabile (warehouse beetle), and Zabrus tenebioides.

In other embodiments, the method of the present disclosure may also beused to control members of the Order Dermaptera (earwigs).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Dictyoptera (cockroaches)including, but is not limited to, Blattella germanica (Germancockroach), Blatta orientalis (oriental cockroach), Parcoblattapennylvanica, Periplaneta americana (American cockroach), Periplanetaaustraloasiae (Australian cockroach), Periplaneta brunnea (browncockroach), Periplaneta fuliginosa (smokybrown cockroach), Pyncoselussuninamensis (Surinam cockroach), and Supella longipalpa (brownbandedcockroach).

In further embodiments, the method of the present disclosure may be usedto control members of the Order Diptera (true flies) including, but isnot limited to, Aedes spp. (mosquitoes), Agromyza frontella (alfalfablotch leafminer), Agromyza spp. (leaf miner flies), Anastrepha spp.(fruit flies), Anastrepha suspensa (Caribbean fruit fly), Anopheles spp.(mosquitoes), Bactrocera spp. (fruit flies), Bactrocera cucurbitae(melon fly), Bactrocera dorsalis (oriental fruit fly), Ceratitis spp.(fruit flies), Ceratitis capitata (Mediterranean fruit fly), Chrysopsspp. (deer flies), Cochliomyia spp. (screwworms), Contarinia spp. (Gallmidges), Culex spp. (mosquitoes), Dasineura spp. (gall midges),Dasineura brassicae (cabbage gall midge), Delia spp., Delia platura(seedcorn maggot), Drosophila spp. (vinegar flies), Fannia spp. (filthflies), Fannia canicularis (little house fly), Fannia scalaris (latrinefly), Gasterophilus intestinalis (horse bot fly), Gracillia perseae,Haematobia irritans (horn fly), Hylemyia spp. (root maggots), Hypodermalineatum (common cattle grub), Liriomyza spp. (leafminer flies),Liriomyza brassica (serpentine leafminer), Liriomyza sativae (vegetableleafminer), Melophagus ovinus (sheep ked), Musca spp. (muscid flies),Musca autumnalis (face fly), Musca domestica (house fly), Oestrus ovis(sheep bot fly), Oscinella frit (frit fly), Pegomyia betae (beetleafminer), Phorbia spp., Psila rosae (carrot rust fly), Rhagoletiscerasi (cherry fruit fly), Rhagoletis pomonella (apple maggot),Sitodiplosis mosellana (orange wheat blossom midge), Stomoxys calcitrans(stable fly), Tabanus spp. (horse flies), and Tipu/a spp. (crane flies).

In other embodiments, the method of the present disclosure may be usedto control members of the Order Hemiptera Sub-order Heteroptera (truebugs) including, but is not limited to, Acrosternum hilare (green stinkbug), Blissus leucopterus (chinch bug), Bragada hilaris, Calocorisnorvegicus (potato mirid), Cimex hemipterus (tropical bed bug), Cimexlectularius (bed bug), Dagbertus fasciatus, Dichelops furcatus,Dysdercus suturellus (cotton stainer), Edessa meditabunda, Eurygastermaura (cereal bug), Euschistus heros, Euschistus servus (brown stinkbug), Helopeltis antonii, Helopeltis theivora (tea blight plantbug),Lagynotomus spp. (stink bugs), Leptocorisa oratorius, Leptocorisavaricornis, Lygus spp. (plant bugs), Lygus hesperus (western tarnishedplant bug), Lygus lineolaris (tarnished plant bug), Maconellicoccushirsutus, Neurocolpus longirostris, Nezara viridula (southern greenstink bug), Phytocoris spp. (plant bugs), Phytocoris californicus,Phytocoris relativus, Piezodorus guildinii (redbanded stink bug),Poecilocapsus lineatus (fourlined plant bug), Psallus vaccinicola,Pseudacysta perseae, Scaptocoris castanea, and Triatoma spp.(bloodsucking conenose bugs/kissing bugs).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Hemiptera, Sub-ordersAuchenorrhyncha (Free-living Hemipterans) and Sternorrhyncha(Plant-parasitic Hemipterans) (aphids, scales, whiteflies, leaflhoppers)including, but is not limited to, Acrythosiphon pisum (pea aphid),Adelges spp. (adelgids), Aleurodes proletella (cabbage whitefly),Aleurodicus disperses, Aleurothrixus floccosus (woolly whitefly),Aluacaspis spp., Amrasca bigutella bigutella, Aphrophora spp.(leafhoppers), Aonidiella aurantii (California red scale), Aphis spp.(aphids), Aphis gossypii (cotton aphid), Aphis pomi (apple aphid),Aulacorthum solani (foxglove aphid), Bemisia spp. (whiteflies), Bemisiaargentifolii, Bemisia tabaci (sweetpotato whitefly), Brachycolus noxius(Russian aphid), Brachycorynella asparagi (asparagus aphid), Brevenniarehi, Brevicoryne brassicae (cabbage aphid), Ceroplastes spp. (scales),Ceroplastes rubens (red wax scale), Chionaspis spp. (scales),Chrysomphalus spp. (scales), Chrysomphalus aonidum (Florida red scale)Coccus spp. (scales), Coccus pseudomagnoliarum (citricola scale),Dysaphis plantaginea (rosy apple aphid), Empoasca spp. (leafhoppers),Eriosoma lanigerum (woolly apple aphid), Icerya purchasi (cottonycushion scale), Idioscopus nitidulus (mango leafhopper), Laodelphaxstriatellus (smaller brown planthopper), Lepidosaphes spp., Macrosiphumspp., Macrosiphum euphorbiae (potato aphid), Macrosiphum granarium(English grain aphid), Macrosiphum rosae (rose aphid), Macrostelesquadrilineatus (aster leafhopper), Mahanarva frimbiolata, Metopolophiumdirhodum (rose grain aphid), Mictis longicornis, Myzus spp., Myzuspersicae (green peach aphid), Nephotettix spp. (leafhoppers),Nephotettix cinctipes (green leafhopper), Nilaparvata lugens (brownplanthopper), Paratrioza cockerelli (tomato psyllid), Parlatoriapergandii (chaff scale), Parlatoria ziziphi (ebony scale), Peregrinusmaidis (corn delphacid), Philaenus spp. (spittlebugs), Phylloxeravitifoliae (grape phylloxera), Physokermes piceae (spruce bud scale),Planococcus spp. (mealybugs), Planococcus citri (citrus mealybug),Planococcus ficus (grape mealybug), Pseudococcus spp. (mealybugs),Pseudococcus brevipes (pine apple mealybug), Quadraspidiotus perniciosus(San Jose scale), Rhopalosiphum spp. (aphids), Rhopalosiphum maidis(corn leaf aphid), Rhopalosiphum padi (oat bird-cherry aphid), Saissetiaspp. (scales), Saissetia oleae (black scale), Schizaphis graminum(greenbug), Sitobion avenae (English grain aphid), Sogatella furcifera(white-backed planthopper), Therioaphis spp. (aphids), Toumeyella spp.(scales), Toxoptera spp. (aphids), Trialeurodes spp. (whiteflies),Trialeurodes vaporariorum (greenhouse whitefly), Trialeurodesabutiloneus (bandedwing whitefly), Unaspis spp. (scales), Unaspisyanonensis (arrowhead scale), and Zulia entreriana. In at least someembodiments, the method of the present disclosure may be used to controlMyzus persicae.

In other embodiments, the method of the present disclosure may be usedto control members of the Order Hymenoptera (ants, wasps, and sawflies)including, but not limited to, Acromyrrmex spp., Athalia rosae, Attaspp. (leafcutting ants), Camponotus spp. (carpenter ants), Diprion spp.(sawflies), Formica spp. (ants), Iridomyrmex humilis (Argentine ant),Monomorium spp., Monomorium minumum (little black ant), Monomoriumpharaonis (Pharaoh ant), Neodiprion spp. (sawflies), Pogonomyrmex spp.(harvester ants), Polistes spp. (paper wasps), Solenopsis spp. (fireants), Tapoinoma sessile (odorous house ant), Tetranomorium spp.(pavement ants), Vespula spp. (yellow jackets), and Xylocopa spp.(carpenter bees).

In certain embodiments, the method of the present disclosure may be usedto control members of the Order Isoptera (termites) including, but notlimited to, Coptotermes spp., Coptotermes curvignathus, Coptotermesfrenchii, Coptotermes formosanus (Formosan subterranean termite),Cornitermes spp. (nasute termites), Cryptotermes spp. (drywoodtermites), Heterotermes spp. (desert subterranean termites),Heterotermes aureus, Kalotermes spp. (drywood termites), Incistitermesspp. (drywood termites), Macrotermes spp. (fungus growing termites),Marginitermes spp. (drywood termites), Microcerotermes spp. (harvestertermites), Microtermes obesi, Procornitermes spp., Reticulitermes spp.(subterranean termites), Reticulitermes banyulensis, Reticulitermesgrassei, Reticulitermes flavipes (eastern subterranean termite),Reticulitermes hageni, Reticulitermes hesperus (western subterraneantermite), Reticulitermes santonensis, Reticulitermes speratus,Reticulitermes tibialis, Reticulitermes virginicus, Schedorhinotermesspp., and Zootermopsis spp. (rotten-wood termites).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Lepidoptera (moths and butterflies)including, but not limited to, Achoea janata, Adoxophyes spp.,Adoxophyes orana, Agrotis spp. (cutworms), Agrotis ipsilon (blackcutworm), Alabama argillacea (cotton leafworm), Amorbia cuneana,Amyelosis transitella (navel orangeworm), Anacamptodes defectaria,Anarsia lineatella (peach twig borer), Anomis sabulifera (jute looper),Anticarsia gemmatalis (velvetbean caterpillar), Archips argyrospila(fruittree leafroller), Archips rosana (rose leaf roller), Argyrotaeniaspp. (tortricid moths), Argyrotaenia citrana (orange tortrix),Autographa gamma, Bonagota cranaodes, Borbo cinnara (rice leaf folder),Bucculatrix thurberiella (cotton leafperforator), Caloptilia spp. (leafminers), Capua reticulana, Carposina niponensis (peach fruit moth),Chilo spp., Chlumetia transversa (mango shoot borer), Choristoneurarosaceana (obliquebanded leafroller), Chrysodeixis spp., Cnaphalocerusmedinalis (grass leafroller), Colias spp., Conpomorpha cramerella,Cossus cossus (carpenter moth), Crambus spp. (Sod webworms),Cydiafunebrana (plum fruit moth), Cydia molesta (oriental fruit moth),Cydia nignicana (pea moth), Cydia pomonella (codling moth), Darnadiducta, Diaphania spp. (stem borers), Diatraea spp. (stalk borers),Diatraea saccharalis (sugarcane borer), Diatraea graniosella(southwester corn borer), Earias spp. (bollworms), Earias insulata(Egyptian bollworm), Earias vitella (rough northern bollworm),Ecdytopopha aurantianum, Elasmopalpus lignosellus (lesser cornstalkborer), Epiphysias postruttana (light brown apple moth), Ephestia spp.(flour moths), Ephestia cautella (almond moth), Ephestia elutella(tobbaco moth), Ephestia kuehniella (Mediterranean flour moth), Epimecesspp., Epinotia aporema, Erionota thrax (banana skipper), Eupoeciliaambiguella (grape berry moth), Euxoa auxiliaris (army cutworm), Feltiaspp. (cutworms), Gortyna spp. (stemborers), Grapholita molesta (orientalfruit moth), Hedylepta indicata (bean leaf webber), Helicoverpa spp.(noctuid moths), Helicoverpa armigera (cotton bollworm), Helicoverpa zea(bollworm/corn earworm), Heliothis spp. (noctuid moths), Heliothisvirescens (tobacco budworm), Hellula undalis (cabbage webworm),Indarbela spp. (root borers), Keiferia lycopersicella (tomato pinworm),Leucinodes orbonalis (eggplant fruit borer), Leucoptera malifoliella,Lithocollectis spp., Lobesia botrana (grape fruit moth), Loxagrotis spp.(noctuid moths), Loxagrotis albicosta (western bean cutworm), Lymantriadispar (gypsy moth), Lyonetia clerkella (apple leaf miner), Mahasenacorbetti (oil palm bagworm), Malacosoma spp. (tent caterpillars),Mamestra brassicae (cabbage armyworm), Maruca testulalis (bean podborer), Metisa plana (bagworm), Mythimna unipuncta (true armyworm),Neoleucinodes elegantalis (small tomato borer), Nymphula depunctalis(rice caseworm), Operophthera brumata (winter moth), Ostrinia nubilalis(European corn borer), Oxydia vesulia, Pandemis cerasana (common curranttortrix), Pandemis heparana (brown apple tortrix), Papilio demodocus,Pectinophora gossypiella (pink bollworm), Peridroma spp. (cutworms),Peridroma saucia (variegated cutworm), Perileucoptera coffeella (whitecoffee leafminer), Phthorimaea operculella (potato tuber moth),Phyllocnisitis citrella, Phyllonorycter spp. (leafminers), Pieris rapae(imported cabbageworm), Plathypena scabra, Plodia interpunctella (Indianmeal moth), Plutella xylostella (diamondback moth), Polychrosis viteana(grape berry moth), Prays endocarps, Prays oleae (olive moth),Pseudaletia spp. (noctuid moths), Pseudaletia unipunctata (armyworm),Pseudoplusia includens (soybean looper), Rachiplusia nu, Scirpophagaincertulas, Sesamia spp. (stemborers), Sesamia inferens (pink rice stemborer), Sesamia nonagrioides, Setora nitens, Sitotroga cerealella(Angoumois grain moth), Sparganothis pilleriana, Spodoptera spp.(armyworms), Spodoptera exigua (beet armyworm), Spodoptera fugiperda(fall armyworm), Spodoptera oridania (southern armyworm), Synanthedonspp. (root borers), Thecla basilides, Thermisia gemmatalis, Tineolabisselliella (webbing clothes moth), Trichoplusia ni (cabbage looper),Tuta absoluta, Yponomeuta spp., Zeuzera coffeae (red branch borer), andZeuzera pyrina (leopard moth). In at least some embodiments, the methodof the present disclosure may be used to control Spodoptera exigua.

The method of the present disclosure may be used to also control membersof the Order Mallophaga (chewing lice) including, but not limited to,Bovicola ovis (sheep biting louse), Menacanthus stramineus (chicken bodylouse), and Menopon gallinea (common hen louse).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Orthoptera (grasshoppers, locusts,and crickets) including, but not limited to, Anabrus simplex (Mormoncricket), Gryllotalpidae (mole crickets), Locusta migratoria, Melanoplusspp. (grasshoppers), Microcentrum retinerve (angularwinged katydid),Pterophylla spp. (kaydids), chistocerca gregaria, Scudderia furcata(forktailed bush katydid), and Valanga nigricorni.

In other embodiments, the method of the present disclosure may be usedto control members of the Order Phthiraptera (sucking lice) including,but not limited to, Haematopinus spp. (cattle and hog lice), Linognathusovillus (sheep louse), Pediculus humanus capitis (human body louse),Pediculus humanus humanus (human body lice), and Pthirus pubis (crablouse).

In particular embodiments, the method of the present disclosure may beused to control members of the Order Siphonaptera (fleas) including, butnot limited to, Ctenocephalides canis (dog flea), Ctenocephalides felis(cat flea), and Pulex irritans (human flea).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Thysanoptera (thrips) including,but not limited to, Caliothrips fasciatus (bean thrips), Caliothripsphaseoli, Frankliniella fusca (tobacco thrips), Frankliniellaoccidentalis (western flower thrips), Frankliniella shultzei,Frankliniella williamsi (corn thrips), Heliothfips haemorrhaidalis(greenhouse thrips), Riphiphorothrips cruentatus, Scirtothrips spp.,Scirtothrips citri (citrus thrips), Scirtothrips dorsalis (yellow teathrips), Taeniothrips rhopalantennalis, Thrips spp., Thrips tabaci(onion thrips), and Thrips hawaiiensis (Hawaiian flower thrips).

The method of the present disclosure may be used to also control membersof the Order Thysanura (bristletails) including, but not limited to,Lepisma spp. (silverfish) and Thermobia spp. (firebrats).

In further embodiments, the method of the present disclosure may be usedto control members of the Order Acari (mites and ticks) including, butnot limited to, Acarapsis woodi (tracheal mite of honeybees), Acarusspp. (food mites), Acarus siro (grain mite), Aceria mangiferae (mangobud mite), Aculops spp., Aculops lycopersici (tomato russet mite),Aculops pelekasi, Aculus pelekassi, Aculus schlechtendali (apple rustmite), Amblyomma americanum (lone star tick), Boophilus spp. (ticks),Brevipalpus obovatus (privet mite), Brevipalpus phoenicis (red and blackflat mite), Demodex spp. (mange mites), Dermacentor spp. (hard ticks),Dermacentor variabilis (american dog tick), Dermatophagoidespteronyssinus (house dust mite), Eotetranycus spp., Eotetranychuscarpini (yellow spider mite), Epitimerus spp., Eriophyes spp., Ixodesspp. (ticks), Metatetranycus spp., Notoedres cati, Oligonychus spp.,Oligonychus coffee, Oligonychus ilicus (southern red mite), Panonychusspp., Panonychus citri (citrus red mite), Panonychus ulmi (European redmite), Phyllocoptruta oleivora (citrus rust mite), Polyphagotarsonemunlatus (broad mite), Rhipicephalus sanguineus (brown dog tick),Rhizoglyphus spp. (bulb mites), Sarcoptes scabiei (itch mite),Tegolophus perseaflorae, Tetranychus spp., Tetranychus urticae(twospotted spider mite), and Varroa destructor (honey bee mite).

In additional embodiments, the method of the present disclosure may beused to control members of the Order Nematoda (nematodes) including, butnot limited to, Aphelenchoides spp. (foliar nematodes), Belonolaimusspp. (sting nematodes), Criconemella spp. (ring nematodes), Dirofilariaimmitis (dog heartworm), Ditylenchus spp. (stem and bulb nematodes),Heterodera spp. (cyst nematodes), Heterodera zeae (corn cyst nematode),Hirschmanniella spp. (root nematodes), Hoplolaimus spp. (lancenematodes), Meloidogyne spp. (root knot nematodes), Meloidogyneincognita (root knot nematode), Onchocerca volvulus (hook-tail worm),Pratylenchus spp. (lesion nematodes), Radopholus spp. (burrowingnematodes), and Rotylenchus reniformis (kidney-shaped nematode).

In at least some embodiments, the method of the present disclosure maybe used to control at least one insect in one or more of the OrdersLepidoptera, Coleoptera, Hemiptera, Thysanoptera, Isoptera, Orthoptera,Diptera, Hymenoptera, and Siphonaptera, and at least one mite in theOrder Acari.

In some embodiments, the method of controlling an insect may compriseapplying a pesticidal composition near a population of insects, whereinthe pesticidal composition comprises a synergistically effective amountof a pyrethroid-based or pyrethrin-based sodium channel modulatorcompound in combination with a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof, and wherein theinsect includes chewing insects, sucking insects, or a mixture thereof.

In other embodiments, the method of controlling an insect may compriseapplying a pesticidal composition near a population of insects, whereinthe pesticidal composition comprises a synergistically effective amountof a pyrethroid-based or pyrethrin-based sodium channel modulatorcompound in combination with a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof, and wherein theinsects are Western flower thrips, Frankliniella occidentalis(Pergande), cotton aphid, Aphis gossypii (Glover), brown stink bug,Euschistus serous (Say), Lygus bug, Lygus hesperus (Knight), or mixturesthereof.

In further embodiments, the method of controlling an insect may compriseapplying a pesticidal composition near a population of insects, whereinthe pesticidal composition comprises a synergistically effective amountof the pesticide selected from (I), (II), or any agriculturallyacceptable salt thereof and at least one of lambda-cyhalothrin,acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin,bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer,bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin,theta-cypermethrin, zeta-cypermethrin, cyphenothrin[(1R)-trans-isomers], deltamethrin, empenthrin [(EZ)-(1R)-isomers],esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate,flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadethrin,permethrin, phenothrin [(1R)-trans-isomer], prallethrin, pyrethrins(pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethrin,tetramethrin [(1R)-isomers], tralomethrin and transfluthrin, wherein theinsects are Western flower thrips, Frankliniella occidentalis(Pergande), cotton aphid, Aphis gossypii (Glover), brown stink bug,Euschistus serous (Say), Lygus bug, Lygus hesperus (Knight), or mixturesthereof.

In one embodiment of the present disclosure, the pesticidal compositionmay be used in conjunction (such as, in a compositional mixture, or asimultaneous or sequential application) with one or more compoundshaving acaricidal, algicidal, avicidal, bactericidal, fungicidal,herbicidal, insecticidal, molluscicidal, nematicidal, rodenticidal,and/or virucidal properties.

In one embodiment of the present disclosure, the pesticidal compositionmay be used in conjunction (such as, in a compositional mixture, or asimultaneous or sequential application) with one or more compounds thatare antifeedants, bird repellents, chemosterilants, herbicide safeners,insect attractants, insect repellents, mammal repellents, matingdisrupters, plant activators, plant growth regulators, and/orsynergists.

The pesticidal compositions of the present disclosure show a synergisticeffect, providing superior pest control at lower pesticidally effectiveamounts of the combined active compounds than when a pyrethroid-based orpyrethrin-based sodium channel modulator compound, or a pesticideselected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide (I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof is used alone.

The pesticidal compositions of the present disclosure may have highsynergistic pest control and allow for a lower effective dosage rate, anincreased environmental safety, and a reduced incidence of pestresistance.

The following examples serve to explain embodiments of the presentinvention in more detail. These examples should not be construed asbeing exhaustive or exclusive as to the scope of this disclosure.

EXAMPLES Example 1 Preparation of3-((3,3,3-trifluoropropyl)thio)propanoyl chloride

A dry five-liter round bottom flask equipped with magnetic stirrer,nitrogen inlet, reflux condenser, and thermometer, was charged with3-((3,3,3-trifluoropropyl)thio)propanoic acid (prepared as described inthe PCT Publication No. WO 2013/062981 to Niyaz et al.) (188 g, 883mmol) in dichloromethane (CH₂Cl₂) (3 L). Thionyl chloride (525 g, 321mL, 4.42 mol) was added dropwise over 50 minutes. The reaction mixturewas heated to reflux (about 36° C.) for two hours, then cooled to roomtemperature (about 22° C.). The resulting mixture was concentrated undervacuum on a rotary evaporator, followed by distillation (40 Torr,product collected at a temperature of from about 123° C. to about 127°C.) to provide the title compound as a clear colorless liquid (177.3 g,86%): ¹H NMR (400 MHz, CDCl₃) δ 3.20 (t, J=7.1 Hz, 2H), 2.86 (t, J=7.1Hz, 2H), 2.78-2.67 (m, 2H), 2.48-2.31 (m, 2H); ¹⁹F NMR (376 MHz, CDCl₃)δ −66.42, −66.43, −66.44, −66.44.

Example 2 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I)

To a solution of 3-chloro-N-ethyl-1-(pyridin-3-yl)-1H-pyrazol-4-amine(prepared as described in the U.S. Publication No. 2012/0110702 to Yapet al.) (10 g, 44.9 mmol) in CH₂Cl₂ (100 mL) at a temperature of about0° C. and under N₂ was added pyridine (5.45 mL, 67.4 mmol),4-dimethylaminopyridine (DMAP) (2.74 g, 22.45 mmol), and3-((3,3,3-trifluoropropyl)thio) propanoyl chloride (9.91 g, 44.9 mmol),sequentially. The reaction was warmed to room temperature and stirredfor one hour. The reaction mixture was poured into water (100 mL), andthe resulting mixture was stirred for five minutes. The mixture wastransferred to a separatory funnel, and the layers were separated. Theaqueous phase was extracted with CH₂Cl₂ (3x50 mL), and the combinedorganic extracts were dried over sodium sulfate (Na₂SO₄), filtered, andconcentrated in vacuo. The crude product was purified via normal phaseflash chromatography (0% to 100% EtOAc/CH₂Cl₂) to provide the desiredproduct as a pale yellow solid (17.21 g, 89%): IR (thin film) 1659 cm⁻¹;¹H NMR (400 MHz, CDCl₃) δ 8.95 (d, J=2.6 Hz, 1H), 8.63 (dd, J=4.7, 1.3Hz, 1H), 8.05 (ddd, J=8.3, 2.7, 1.4 Hz, 1H), 7.96 (s, 1H), 7.47 (dd,J=8.3, 4.8 Hz, 1H), 3.72 (q, J=7.1 Hz, 2H), 2.84 (t, J=7.2 Hz, 2H), 2.66(m, 2H), 237 (t, J=7.2 Hz, 2H), 2.44 (m, 2H), 1.17 (t, J=7.2 Hz, 3H);ESIMS m/z 409 ([M+2H]⁺).

Example 3 Preparation ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-(3,3,3-trifluoropropyl)sulfinyl)propanamide(II)

To a solution ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I) (500 mg, 1.229 mmol) in hexafluoroisopropanol (5 mL) stirring atroom temperature was added 30% hydrogen peroxide (523 mg, 4.92 mmol).The solution was stirred at room temperature for 15 minutes. It wasquenched with saturated sodium sulfite solution and extracted withCH₂Cl₂. Silica gel chromatography (0%-10% MeOH/CH₂Cl₂) gave the titlecompound as white semi-solid (495 mg, 95%): IR (thin film) 1660 cm⁻¹; ¹HNMR (400 MHz, CDCl₃) δ 8.96 (d, J=2.4 Hz, 1H), 8.64 (dd, J=4.7, 1.4 Hz,1H), 8.07-8.00 (m, 2H), 7.46 (ddd, J=8.3, 4.8, 0.7 Hz, 1H), 3.85-3.61(m, 2H), 3.23-3.08 (m, 1H), 3.03-2.76 (m, 3H), 2.74-2.52 (m, 4H), 1.18(t, J=7.2 Hz, 3H); ESIMS m/z 423 ([M+H]⁺).

Example 4 Determination of the Existence of Synergic Effect

The method described in Colby S. R., “Calculating Synergistic andAntagonistic Responses of Herbicide Combinations,” Weeds, 1967, 15,20-22 was used to determine an existence of synergic effect between thepyrethroid-based or pyrethrin-based sodium channel modulator compoundand the pesticide (I), (II), or any agriculturally acceptable saltthereof in the formulated pesticidal composition. In this method, thepercent insect control of the formulated pesticidal composition asobserved in the study was compared to the “expected” percent control (E)as calculated by equation (1) (hereinafter “Colby's equation”) below:

$\begin{matrix}{E = {X + Y - \left( \frac{XY}{100} \right)}} & (1)\end{matrix}$

where

X is the percentage of control with the first pesticide at a given rate(p),

Y is the percentage of control with the second pesticide at a given rate(q), and

E is the expected control by the first and second pesticide at a rate ofp+q.

If the observed percent control of the formulated pesticidal is greaterthan E, there is a synergistic effect between the pyrethroid-based orpyrethrin-based sodium channel modulator compound and the pesticide (I),(II), or any agriculturally acceptable salt thereof in the formulatedpesticidal composition. If the observed percent control of theformulated pesticidal is equaled to or less than E, there is nosynergistic effect between the pyrethroid-based or pyrethrin-basedsodium channel modulator compound and the pesticide (I), (II), or anyagriculturally acceptable salt thereof in the formulated pesticidalcomposition.

Example 5 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II) and lambda-Cyhalothrin Against Western flower thrips, Frankliniellaoccidentalis (Pergande)

A pesticidal composition was prepared by thoroughly mixing about 0.04weight % ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide (hereinafter “compound II”) with about 0.02 weight % oflambda-cyhalothrin.

The active compounds were formulated in a 10% acetone solution with0.025% non-ionic surfactant, TWEEN® 20. Cotton leaf punches were usedfor bioassays. Two cotton leaf punches were placed in each solution andleft there for 10 minutes. Leaves were taken out of the solution, placedon a piece of filter paper in separated Petri dishes, and air dried.Each leaf disc was considered a repetition. Five nymph of Western flowerthrips, Frankliniella occidentalis, were infested per repetition. Theassessment of mortality was done three days after infestation. Thepercent control determined three days after the treatment were as shownin table 2. The percent control of the pesticidal composition Westernflower thrips, Frankliniella occidentalis (Pergande), was determined asthe “Observed” action, and compared to those obtained by using about0.04 weight % of compound II, and using about 0.02 weight % oflambda-cyhalothrin alone. The “Colby's Expected Action” was calculatedusing Colby's equation as discussed previously.

TABLE 2 Treatment for Dose Rate % Control Western Flower Thrips (weight%) Three Days After Treatment Compound II 0.04 20% Lambda-Cyhalothrin0.02 0% Compound II (+) Lambda- 0.04 + 0.02 40% Cyhalothrin ObservedAction Compound II (+) Lambda- 0.04 + 0.02 20% Cyhalothrin Colby'sExpected Action Compound II (+) Lambda- 0.04 + 0.02 20% CyhalothrinDifferences: Observed vs. Expected

As shown in table 2, the observed percent control of the pesticidalcomposition against the Western flower thrips (40%) was higher than theexpected percentage control according to Colby's equation (20%). Thepesticidal composition showed 100% improvement over the Colby's expectedaction. Therefore, the pesticidal composition comprising 0.04 weight %of compound II and about 0.02 weight % of lambda-cyhalothrin showedsynergistic effect against the Western flower thrips.

Example 6 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II) and lambda-Cyhalothrin Against Cotton Aphid, Aphis gossypii(Glover)

A pesticidal composition was prepared by thoroughly mixing about 0.002weight % of compound II with about 0.005 weight % of lambda-cyhalothrin.

Cotton plants at cotyledon stage were treated with different activecompounds using track sprayer. Wingless mixed aphid stages of cottonaphid, Aphis gossypii (Glover), were infested onto each plant. Thepercent control determined three days after the treatment were as shownin table 3.

TABLE 3 Treatment Dose Rate % Control for Cotton Aphid (weight %) ThreeDays After Treatment Compound II 0.002 28% Lambda-Cyhalothrin 0.005 0%Compound II (+) 0.002 + 0.005 52% Lambda-Cyhalothrin Observed ActionCompound II (+) 0.002 + 0.005 28% Lambda-Cyhalothrin Colby's ExpectedAction Compound II (+) 0.002 + 0.005 24% Lambda-Cyhalothrin Differences:Observed vs. Expected

As shown in table 3, the observed percent control of the pesticidalcomposition against the cotton aphid (52%) was higher than the expectedpercentage control according to Colby's equation (28%). This was 85%improvement over the Colby's expected action. Therefore, the pesticidalcomposition comprising 0.002 weight % of compound II and about 0.005weight % of lambda-cyhalothrin showed synergistic effect against cottonaphid.

Example 7 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II) and lambda-Cyhalothrin Against Brown Stink Bug, Euschistus herosExample 7A

A pesticidal composition was prepared by thoroughly mixing about 0.04weight % of compound II with about 0.000156 weight % oflambda-cyhalothrin.

The bioassays were performed wherein different active compounds wereapplied to the diet of five second-instar nymphs of brown stink bug,Euschistus heros. The percent control determined after six days of thediet treatment were as shown in table 4.

TABLE 4 Treatment for Dose Rate % Control Brown Stink Bug (weight %)After Six Days of Treatment Compound II 0.04   0% Lambda-Cyhalothrin0.000156 29% Compound II (+) 0.04 + 0.000156 65% Lambda-CyhalothrinObserved Action Compound II (+) 0.04 + 0.000156 29% Lambda-CyhalothrinColby's Expected Action Compound II (+) 0.04 + 0.000156 36%Lambda-Cyhalothrin Differences: Observed vs. Expected

As shown in table 4, the observed percent control of the pesticidalcomposition against brown stink bug (65%) was higher than the expectedpercentage control according to Colby's equation (29%). This was 124%improvement over the Colby's expected action. Therefore, the pesticidalcomposition comprising 0.04 weight % of compound II and about 0.000156weight % of lambda-cyhalothrin showed synergistic effect against brownstink bug.

Example 7B

A pesticidal composition was prepared by thoroughly mixing about 0.04weight % of compound II with about 0.000078 weight % oflambda-cyhalothrin.

The bioassays were performed wherein different active compounds wereapplied to the diet of five second-instar nymphs of brown stink bug,Euschistus heros. The percent control determined after six days of thediet treatment were as shown in table 5.

As shown in table 5, the observed percent control of the pesticidalcomposition against brown stink bug was about 56% after six days oftreatment. On the other hand, compound II and lambda-cyhalothrin, whenused alone, showed no control against brown stink bug, and therefore theexpected percentage control according to Colby's equation was zero.Thus, the pesticidal composition comprising 0.04 weight % of compound IIand 0.000078 weight % of lambda-cyhalothrin showed synergistic effectagainst brown stink bug.

TABLE 5 % Control Treatment for Dose Rate After Six Days Brown Stink Bug(weight %) of Treatment Compound II 0.04   0% Lambda-Cyhalothrin0.000078 0% Compound II (+) Lambda- 0.04 + 0.000078 56% CyhalothrinObserved Action Compound II (+) Lambda- 0.04 + 0.000078 0% CyhalothrinColby's Expected Action Compound II (+) Lambda- 0.04 + 0.000078 56%Cyhalothrin Differences: Observed vs. Expected

Example 8 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II) and lambda-Cyhalothrin Against Lygus bug, Lygus hesperus (Knight)

A pesticidal composition was prepared by thoroughly mixing about 0.04weight % of compound II with about 0.000078 weight % oflambda-cyhalothrin.

String beans were treated with different active compounds for tenminutes. Three four-day old nymphs of Lygus bug, Lygus hesperus(Knight), were infested onto each bean sample. The percent controldetermined after three days of the treatment were as shown in table 6.

TABLE 6 Treatment for Dose Rate % Control Lygus Bugs (weight %) FiveDays After Treatment Compound II 0.04   25% Lambda-Cyhalothrin 0.00007822% Compound II (+) 0.04 + 0.000078 72% Lambda-Cyhalothrin ObservedAction Compound II (+)- 0.04 + 0.000078 41.5%   Lambda CyhalothrinColby's Expected Action Compound II (+) 0.04 + 0.000078 30.5%  Lambda-Cyhalothrin Differences: Observed vs. Expected

As shown in table 6, the observed percent control of the pesticidalcomposition against Lygus bug (72%) was higher than the expectedpercentage control according to Colby's equation (41.5%). This was 73.5%improvement over the Colby's expected action. Therefore, the pesticidalcomposition comprising 0.04 weight % of compound II and about 0.000078weight % of lambda-cyhalothrin showed synergistic effect against Lygusbug.

Example 9 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I) and lambda-Cyhalothrin Against Brown Stink Bugs, Euschistus heros

A pesticidal composition was prepared by thoroughly mixing about 0.04weight % of compound I with about 0.0025 weight % of lambda-cyhalothrin.

The active compounds were formulated in a 10% acetone solution with0.025% non-ionic surfactant, TWEEN® 20. Bioassays were performed foreach different active solution. Bean pieces (about one inch-long) wereused for the tests. Four bean pieces were placed in each tested activesolution and left there for 10 minutes. Bean pieces were taken out ofthe active solution, and each piece was placed in a well in a 32-welltray and allowed to air dry. Three third-instar nymphs of brown stinkbug, Euschistus heros, were infested into each well. The percent controldetermined after four days of the treatment were as shown in table 7.The percent control of the pesticidal composition against brown stinkbug, Euschistus heros, was determined as the “Observed” action, andcompared to those obtained by using about 0.04 weight % of compound I,and using about 0.0025 weight % of lambda-cyhalothrin alone. The“Colby's Expected Action” was calculated using Colby's equation asdiscussed previously.

TABLE 7 % Control Treatment for Dose Rate Four Days Brown Stink Bug(weight %) After Treatment Compound I 0.04  17% Lambda-Cyhalothrin0.0025 67% Compound I (+) Lambda-Cyhalothrin 0.04 + 0.0025 92% ObservedAction Compound I (+) Lambda-Cyhalothrin 0.04 + 0.0025 72.61%   Colby'sExpected Action Compound I (+) Lambda-Cyhalothrin 0.04 + 0.0025 19.39%  Differences: Observed vs. Expected

As shown in table 7, the observed percent control of the pesticidalcomposition against brown stink bug (92%) was higher than the expectedpercentage control according to Colby's equation (72.61%). This was 26%improvement over the Colby's expected action. Therefore, the pesticidalcomposition comprising 0.04 weight % of compound I and about 0.0025weight % of lambda-cyhalothrin showed synergistic effect against brownstink bug, Euschistus heros.

Example 10 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I) and lambda-Cyhalothrin Against Brown Stink Bugs, Euschistus servus(Say) Example 10A

An emulsifying concentrate pesticidal composition comprising 0.0306weight % of compound I and about 0.0122 weight % of lambda-cyhalothrinwas diluted and applied to the field using a spray volume of 327 L/ha.Dyne-Amic at 0.625% V/V was used as an adjuvant in the tank mix, and theapplication was done using a backpack sprayer. Trial was conducted undera natural stink bug infestation. Numbers of adults and nymphs werecounted four days after application in 1.82 meters of row per plot usinga shake sheet (0.91 meters by 2 rows).

The percent control determined after four days of the treatment were asshown in table 8. The percent control of the pesticidal compositionagainst brown stink bugs, Euschistus servus, was determined as the“Observed” action, and compared to those obtained by using about 0.0306weight % of compound I, and using about 0.0122 weight % oflambda-cyhalothrin alone. The “Colby's Expected Action” was calculatedusing Colby's equation as discussed previously.

As shown in table 8, the observed percent control of the pesticidalcomposition against brown stink bug, Euschistus servus (Say), (84.85%)was higher than the expected percentage control according to Colby'sequation (15.15%). This was about 460% improvement over the Colby'sexpected action. Therefore, the pesticidal composition comprising 0.0306weight % of compound I and about 0.0122 weight % of lambda-cyhalothrinshowed significant synergistic effect against brown stink bug,Euschistus servus, for field test.

TABLE 8 % Control Four Days Treatment for Dose Rate After Brown StinkBug (weight %) Treatment Compound I 0.0306 15.15% Lambda-Cyhalothrin0.0122    0% Compound I (+) Lambda-Cyhalothrin 0.0306 + 0.0122 84.85%Observed Action Compound I (+) Lambda-Cyhalothrin 0.0306 + 0.0122 15.15%Colby's Expected Action Compound I (+) Lambda-Cyhalothrin 0.0306 +0.0122 69.70% Differences: Observed vs. Expected

As shown in table 8, the observed percent control of the pesticidalcomposition against brown stink bug, Euschistus servus (Say), (84.85%)was higher than the expected percentage control according to Colby'sequation (15.15%). This was about 460% improvement over the Colby'sexpected action. Therefore, the pesticidal composition comprising 0.0306weight % of compound I and about 0.0122 weight % of lambda-cyhalothrinshowed significant synergistic effect against brown stink bug,Euschistus servus (Say), for field test.

Example 10B

An emulsifying concentrate pesticidal composition comprising 0.0306weight % of compound I and about 0.0183 weight % of lambda-cyhalothrinwas diluted and used for a field test against brown stink bug,Euschistus servus (Say), according to the procedure described in Example10A.

The percent control determined four days after the treatment were asshown in table 9. The percent control of the pesticidal compositionagainst brown stink bug, Euschistus servus (Say), was determined as the“Observed” action, and compared to those obtained by using about 0.0306weight % of compound I, and using about 0.0183 weight % oflambda-cyhalothrin alone. The “Colby's Expected Action” was calculatedusing Colby's equation as discussed previously.

TABLE 9 % Control Four Days Treatment for Dose Rate After Brown StinkBug (weight %) Treatment Compound I 0.0306 15.15% Lambda-Cyhalothrin0.0183  54.5% Compound I (+) Lambda-Cyhalothrin 0.0306 + 0.0183 75.76%Observed Action Compound I (+) Lambda-Cyhalothrin 0.0306 + 0.0183 61.44%Colby's Expected Action Compound I (+) Lambda-Cyhalothrin 0.0306 +0.0183 14.32% Differences: Observed vs. Expected

As shown in table 9, the observed percent control of the pesticidalcomposition against brown stink bug (75.76%) was higher than theexpected percentage control according to Colby's equation (61.44%). Thiswas about 23% improvement over the Colby's expected action. Therefore,the pesticidal composition comprising 0.0306 weight % of compound I andabout 0.0183 weight % of lambda-cyhalothrin showed synergistic effectagainst brown stink bug, Euschistus servus (Say), for field test.

Example 10C

An emulsifying concentrate pesticidal composition comprising 0.0459weight % of compound I and about 0.0122 weight % of lambda-cyhalothrinwas diluted and used for a field test against brown stink bug,Euschistus servus (Say), according to the procedure described in example10A.

The percent control determined four days after the treatment were asshown in table 10. The percent control of the pesticidal compositionagainst brown stink bug, Euschistus servus (Say), was determined as the“Observed” action, and compared to those obtained by using about 0.0459weight % of compound I, and using about 0.0122 weight % oflambda-cyhalothrin alone. The “Colby's Expected Action” was calculatedusing Colby's equation as discussed previously.

As shown in table 10, the observed percent control of the pesticidalcomposition against brown stink bug (60.6%) was higher than the expectedpercentage control according to Colby's equation (15.15%). This wasabout 300% improvement over the Colby's expected action. Therefore, thepesticidal composition comprising 0.0459 weight % of compound I andabout 0.0122 weight % of lambda-cyhalothrin showed significantsynergistic effect against brown stink bug, Euschistus servus (Say), forfield test.

TABLE 10 % Control Four Days Treatment for Dose Rate After Brown StinkBug (weight %) Treatment Compound I 0.0459 15.15% Lambda-Cyhalothrin0.0122    0% Compound I (+) Lambda-Cyhalothrin 0.0459 + 0.0122  60.6%Observed Action Compound I (+) Lambda-Cyhalothrin 0.0459 + 0.0122 15.15%Colby's Expected Action Compound I (+) Lambda-Cyhalothrin 0.0459 +0.0122 45.45% Differences: Observed vs. Expected

Example 11 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I) and lambda-Cyhalothrin Against Green Stink Bugs, Nezara viridulaExample 11A

An emulsifying concentrate pesticidal composition comprising 0.0306weight % of compound I and about 0.0122 weight % of lambda-cyhalothrinwas diluted and applied to the field using a spray volume of 327 L/ha.Dyne-Amic at 0.625% V/V was used as an adjuvant in the tank mix, and theapplication was done using a backpack sprayer. Trial was conducted undera natural stink bug infestation. Numbers of adults and nymphs werecounted four days after application in 1.82 meters of row per plot usinga shake sheet (0.91 meters by 2 rows).

The percent control determined four days after the treatment were asshown in table 11. The percent control of the pesticidal compositionagainst green stink bugs, Nezara viridula, was determined as the“Observed” action, and compared to those obtained by using about 0.0306weight % of compound I, and using about 0.0122 weight % oflambda-cyhalothrin alone. The “Colby's Expected Action” was calculatedusing Colby's equation as discussed previously.

TABLE 11 % Control Four Days Treatment for Dose Rate After Green StinkBug (weight %) Treatment Compound I 0.0306  7.39% Lambda-Cyhalothrin0.0122 97.54% Compound I (+) Lambda-Cyhalothrin 0.0306 + 0.0122   100%Observed Action Compound I (+) Lambda-Cyhalothrin 0.0306 + 0.0122 97.72%Colby's Expected Action Compound I (+) Lambda-Cyhalothrin 0.0306 +0.0122  2.28% Differences: Observed vs. Expected

As shown in table 11, the observed percent control of the pesticidalcomposition against green stink bugs, Nezara viridula, (100%) was higherthan the expected percentage control according to Colby's equation(97.72%). This was about 2% improvement over the Colby's expectedaction. Therefore, the pesticidal composition comprising 0.0306 weight %of compound I and about 0.0122 weight % of lambda-cyhalothrin showedsignificant synergistic effect against green stink bugs, Nezaraviridula, for field test.

Example 11B

An emulsifying concentrate pesticidal composition comprising 0.0306weight % of compound I and about 0.0183 weight % of lambda-cyhalothrinwas diluted and used for a field test against green stink bugs, Nezaraviridula, according to the procedure described in example 11A. Thepercent control determined four days after the treatment were as shownin table 12.

As shown in table 12, the observed percent control of the pesticidalcomposition against green stink bugs (100%) was higher than the expectedpercentage control according to Colby's equation (92.11%). This wasabout 8.6% improvement over the Colby's expected action. Therefore, thepesticidal composition comprising 0.0306 weight % of compound I andabout 0.0183 weight % of lambda-cyhalothrin showed significantsynergistic effect against green stink bugs, Nezara viridula, for fieldtest.

TABLE 12 % Control Four Days Treatment for Dose Rate After Green StinkBug (weight %) Treatment Compound I 0.0306 11.94% Lambda-Cyhalothrin0.0183 91.04% Compound I (+) Lambda-Cyhalothrin 0.0306 + 0.0183   100%Observed Action Compound I (+) Lambda-Cyhalothrin 0.0306 + 0.0183 92.11%Colby's Expected Action Compound I (+) Lambda-Cyhalothrin 0.0306 +0.0183  7.89% Differences: Observed vs. Expected

Example 12 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II) and lambda-Cyhalothrin Against Stink Bugs, Edessa meditabunda,Euschistus heros, and Piezodorus guildinii Example 12A

An emulsifying concentrate pesticidal composition comprising 0.015weight % of compound II and about 0.027 weight % of lambda-cyhalothrinwas diluted and applied to the field was using a spray volume of 150L/ha. Silwet L-77 at 0.1% V/V was used as an adjuvant in the tank mix,and the application was done using a CO₂ backpack sprayer. Trial wasconducted under a natural stink bug infestation. Numbers of adults andnymphs were counted two days after application in 2.0 meters of row perplot using a shake sheet. The stink bug population consisted on about75% Edessa meditabunda, 20% of Euschistus heros, and 5% Piezodorusguildinii.

The percent control determined three days after the treatment were asshown in table 13. As shown in table 13, the observed percent control ofthe pesticidal composition against stink bugs (75%) was higher than theexpected percentage control according to Colby's equation (50.83%). Thiswas about 48% improvement over the Colby's expected action. Therefore,the pesticidal composition comprising 0.10 weight % of compound II andabout 0.027 weight % of lambda-cyhalothrin showed significantsynergistic effect against stink bugs (Edessa meditabunda, Euschistusheros, and Piezodorus guildinii) for field test.

TABLE 13 % Control Treatment for Dose Rate Three Days Stink Bugs (weight%) After Treatment Compound II 0.10   12.5% Lambda-Cyhalothrin 0.027 43.8% Compound II (+) Lambda-Cyhalothrin 0.10 + 0.027   75% ObservedAction Compound II (+) Lambda-Cyhalothrin 0.10 + 0.027 50.83% Colby'sExpected Action Compound II (+) Lambda-Cyhalothrin 0.10 + 0.027 24.17%Differences: Observed vs. Expected

Example 12B

An emulsifying concentrate pesticidal composition comprising 0.13 weight% of compound II and about 0.027 weight % of lambda-cyhalothrin wasdiluted and used for a field test against the stink bug population(about 75% Edessa meditabunda, 20% of Euschistus heros, and 5%Piezodorus guildinii), according to the procedure described in example12A.

The percent control determined three days after the treatment were asshown in table 14.

TABLE 14 % Control Treatment for Dose Rate Three Days Stink Bugs (weight%) After Treatment Compound II 0.13  18.8% Lambda-Cyhalothrin 0.02743.8% Compound II (+) Lambda-Cyhalothrin 0.13 + 0.027 87.5% ObservedAction Compound II (+) Lambda-Cyhalothrin 0.13 + 0.027 54.37%  Colby'sExpected Action Compound II (+) Lambda-Cyhalothrin 0.13 + 0.027 33.13% Differences: Observed vs. Expected

As shown in table 14, the observed percent control of the pesticidalcomposition against stink bugs (87.5%) was higher than the expectedpercentage control according to Colby's equation (54.37%). This wasabout 61% improvement over the Colby's expected action. Therefore, thepesticidal composition comprising 0.13 weight % of compound II and about0.027 weight % of lambda-cyhalothrin showed significant synergisticeffect against stink bugs (Edessa meditabunda, Euschistus heros, andPiezodorus guildinii) for field test.

Example 12C

An emulsifying concentrate pesticidal composition comprising 0.20 weight% of compound II and about 0.027 weight % of lambda-cyhalothrin wasdiluted and used for a field test against the stink bug population(about 75% Edessa meditabunda, 20% of Euschistus heros, and 5%Piezodorus guildinii), according to the procedure described in example12A. The percent control determined three days after the treatment wereas shown in table 15.

TABLE 15 % Control Treatment for Dose Rate Three Days Stink Bugs (weight%) After Treatment Compound II 0.20   6.3% Lambda-Cyhalothrin 0.027 43.8% Compound II (+) Lambda-Cyhalothrin 0.20 + 0.027  87.5% ObservedAction Compound II (+) Lambda-Cyhalothrin 0.20 + 0.027 47.34% Colby'sExpected Action Compound II (+) Lambda-Cyhalothrin 0.20 + 0.027 40.16%Differences: Observed vs. Expected

As shown in table 15, the observed percent control of the pesticidalcomposition against stink bugs (87.5%) was higher than the expectedpercentage control according to Colby's equation (47.34%). This wasabout 85% improvement over the Colby's expected action. Therefore, thepesticidal composition comprising 0.20 weight % of compound II and about0.027 weight % of lambda-cyhalothrin showed significant synergisticeffect against stink bugs (Edessa meditabunda, Euschistus heros, andPiezodorus guildinii) for field test.

Example 13 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I) and lam bda-Cyhalothrin Against Western flower thrips, Frankliniellaoccidentalis Example 13A

A pesticidal composition was prepared by thoroughly mixing about 0.04weight % of compound I with about 0.000078 weight % oflambda-cyhalothrin.

The active compounds were formulated in a 10% acetone solution with0.025% non-ionic surfactant, TWEEN® 20. Cotton leaf punches were usedfor bioassays. Two cotton leaf punches were placed in each solution andleft there for 10 minutes. Leaves were taken out of the solution, placedon a piece of filter paper in separated Petri dishes, and air dried.Each leaf disc was considered a repetition. Five nymph of Western flowerthrips, Frankliniella occidentalis, were infested per repetition. Theassessment of mortality was done three days after infestation.

TABLE 16 % Control Three Days Treatment for Dose Rate After WesternFlower Thrips (weight %) Treatment Compound I 0.04 0% Lambda-Cyhalothrin0.000078 0% Compound I (+) Lambda-Cyhalothrin 0.04 + 0.000078 20% Observed Action Compound I (+) Lambda-Cyhalothrin 0.04 + 0.000078 0%Colby's Expected Action Compound I (+) Lambda-Cyhalothrin 0.04 +0.000078 20%  Differences: Observed vs. Expected

As shown in table 16, compound I and lambda-cyhalothrin, when usedalone, showed no activity against Western flower thrips, Frankliniellaoccidentalis. When about 0.04 weight % of compound I was used incombination with about 0.00002 weight % of lambda-cyhalothrin, about 20%percent control was observed. Therefore, the pesticidal compositioncomprising 0.04 weight % of compound I and about 0.00002 weight % oflambda-cyhalothrin showed synergistic effect against Western flowerthrips, Frankliniella occidentalis.

Example 13B

A pesticidal composition was prepared by thoroughly mixing about 0.04weight % of compound I with about 0.00002 weight % oflambda-cyhalothrin.

The active compounds were formulated in a 10% acetone solution with0.025% non-ionic surfactant, TWEEN® 20. The active formulation weretested against Western flower thrips, Frankliniella occidentalis,according to the procedure described in example 13A. The percent controldetermined three days after the treatment were as shown in table 17.

As shown in table 17, the observed percent control of the pesticidalcomposition against Western flower thrips (40%) was higher than theexpected percentage control according to Colby's equation (10%). Thiswas about 300% improvement over the Colby's expected action. Therefore,the pesticidal composition comprising 0.04 weight % of compound I andabout 0.00002 weight % of lambda-cyhalothrin showed significantsynergistic effect against Western flower thrips, Frankliniellaoccidentalis.

TABLE 17 % Control Three Days Treatment for Dose Rate After WesternFlower Thrips (weight %) Treatment Compound I 0.04  0%Lambda-Cyhalothrin 0.00002 10% Compound I (+) Lambda-Cyhalothrin 0.04 +0.00002 40% Observed Action Compound I (+) Lambda-Cyhalothrin 0.04 +0.00002 10% Colby's Expected Action Compound I (+) Lambda-Cyhalothrin0.04 + 0.00002 30% Differences: Observed vs. Expected

Example 13C

A pesticidal composition was prepared by thoroughly mixing about 0.04weight % of compound I with about 0.0003125 weight % oflambda-cyhalothrin.

The active compounds were formulated in a 10% acetone solution with0.025% non-ionic surfactant, TWEEN® 20. The active formulation weretested against Western flower thrips, Frankliniella occidentalis,according to the procedure described in example 13A. The percent controldetermined three days after the treatment were as shown in table 18.

TABLE 18 % Control Three Days Treatment for Dose Rate After WesternFlower Thrips (weight %) Treatment Compound I 0.04  0%Lambda-Cyhalothrin 0.0003125 10% Compound I (+) Lambda-Cyhalothrin0.04 + 0.0003125 40% Observed Action Compound I (+) Lambda-Cyhalothrin0.04 + 0.0003125 10% Colby's Expected Action Compound I (+)Lambda-Cyhalothrin 0.04 + 0.0003125 30% Differences: Observed vs.Expected

As shown in table 18, the observed percent control of the pesticidalcomposition against Western flower thrips (40%) was higher than theexpected percentage control according to Colby's equation (10%). Thiswas about 300% improvement over the Colby's expected action. Therefore,the pesticidal composition comprising 0.04 weight % of compound I andabout 0.0003125 weight % of lambda-cyhalothrin showed significantsynergistic effect against Western flower thrips, Frankliniellaoccidentalis.

Example 13D

A pesticidal composition was prepared by thoroughly mixing about 0.04weight % of compound I with about 0.00125 weight % oflambda-cyhalothrin.

The active compounds were formulated in a 10% acetone solution with0.025% non-ionic surfactant, TWEEN® 20. The active formulation weretested against Western flower thrips, Frankliniella occidentalis,according to the procedure described in example 13A. The percent controldetermined three days after the treatment were as shown in table 19.

TABLE 19 % Control Three Days Treatment for Dose Rate After WesternFlower Thrips (weight %) Treatment Compound I 0.04  0%Lambda-Cyhalothrin 0.00125 10% Compound I (+) Lambda-Cyhalothrin 0.04 +0.00125 30% Observed Action Compound I (+) Lambda-Cyhalothrin 0.04 +0.00125 10% Colby's Expected Action Compound I (+) Lambda-Cyhalothrin0.04 + 0.00125 20% Differences: Observed vs. Expected

As shown in table 19, the observed percent control of the pesticidalcomposition against Western flower thrips (30%) was higher than theexpected percentage control according to Colby's equation (10%). Thiswas about 200% improvement over the Colby's expected action. Therefore,the pesticidal composition comprising 0.04 weight % of compound I andabout 0.00125 weight % of lambda-cyhalothrin showed significantsynergistic effect against Western flower thrips, Frankliniellaoccidentalis.

Example 13E

A pesticidal composition was prepared by thoroughly mixing about 0.04weight % of compound I with about 0.0050 weight % of lambda-cyhalothrin.

The active compounds were formulated in a 10% acetone solution with0.025% non-ionic surfactant, TWEEN® 20. The active formulation weretested against Western flower thrips, Frankliniella occidentalis,according to the procedure described in example 13A. The percent controldetermined three days after the treatment were as shown in table 20.

As shown in table 20, the observed percent control of the pesticidalcomposition against Western flower thrips (50%) was higher than theexpected percentage control according to Colby's equation (40%). Thiswas about 25% improvement over the Colby's expected action. Therefore,the pesticidal composition comprising 0.04 weight % of compound I andabout 0.0050 weight % of lambda-cyhalothrin showed synergistic effectagainst Western flower thrips, Frankliniella occidentalis.

TABLE 20 % Control Three Days Treatment for Dose Rate After WesternFlower Thrips (weight %) Treatment Compound I 0.04  0%Lambda-Cyhalothrin 0.0050 40% Compound I (+) Lambda-Cyhalothrin 0.04 +0.0050 50% Observed Action Compound I (+) Lambda-Cyhalothrin 0.04 +0.0050 40% Colby's Expected Action Compound I (+) Lambda-Cyhalothrin0.04 + 0.0050 10% Differences: Observed vs. Expected

Example 13F

A pesticidal composition was prepared by thoroughly mixing about 0.04weight % of compound I with about 0.0025 weight % of lambda-cyhalothrin.

The active compounds were formulated in a 10% acetone solution with0.025% non-ionic surfactant, TWEEN® 20. The active formulation weretested against Western flower thrips, Frankliniella occidentalis,according to the procedure described in example 13A. The percent controldetermined three days after the treatment were as shown in table 21.

TABLE 21 % Control Three Days Treatment for Dose Rate After WesternFlower Thrips (weight %) Treatment Compound I 0.04  0%Lambda-Cyhalothrin 0.02 60% Compound I (+) Lambda-Cyhalothrin 0.04 +0.02 70% Observed Action Compound I (+) Lambda-Cyhalothrin 0.04 + 0.0260% Colby's Expected Action Compound I (+) Lambda-Cyhalothrin 0.04 +0.02 10% Differences: Observed vs. Expected

As shown in table 21, the observed percent control of the pesticidalcomposition against Western flower thrips (70%) was higher than theexpected percentage control according to Colby's equation (60%). Thiswas about 17% improvement over the Colby's expected action. Therefore,the pesticidal composition comprising 0.04 weight % of compound I andabout 0.02 weight % of lambda-cyhalothrin showed synergistic effectagainst Western flower thrips, Frankliniella occidentalis.

Example 14 Synergistic Effect of NN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I) and lambda-Cyhalothrin Against Western Plant Bug, Lygus hesperusExample 14A

A pesticidal composition was prepared by thoroughly mixing about 0.04weight % of compound I with about 0.000078 weight % oflambda-cyhalothrin.

The active compounds were formulated in a 10% acetone solution with0.025% non-ionic surfactant, TWEEN® 20. Bean pieces (about oneinch-long) were used for the tests. Four bean pieces were placed in eachtested active solution and left there for 10 minutes. Bean pieces weretaken out of the active solution, and each piece was placed in a well ina 32-well tray and allowed to air dry. Three third-instar nymphs ofWestern plant bug, Lygus hesperus, were infested into each well. Thepercent control determined three days after the treatment were as shownin table 22.

TABLE 22 % Control Three Days Treatment for Dose Rate After Plant Bugs,Lygus hesperus (weight %) Treatment Compound I 0.04  0%Lambda-Cyhalothrin 0.000078 33% Compound I (+) Lambda-Cyhalothrin 0.04 +0.000078 50% Observed Action Compound I (+) Lambda-Cyhalothrin 0.04 +0.000078 33% Colby's Expected Action Compound I (+) Lambda-Cyhalothrin0.04 + 0.000078 17% Differences: Observed vs. Expected

As shown in table 22, the observed percent control of the pesticidalcomposition against plant bugs (50%) was higher than the expectedpercentage control according to Colby's equation (33%). This was about52% improvement over the Colby's expected action. Therefore, thepesticidal composition comprising 0.04 weight % of compound I and about0.000078 weight % of lambda-cyhalothrin showed synergistic effectagainst plant bug, Lygus hesperus.

Example 14B

A pesticidal composition was prepared by thoroughly mixing about 0.04weight % of compound I with about 0.0003125 weight % oflambda-cyhalothrin.

The active compounds formulated in a 10% acetone solution with 0.025%non-ionic surfactant, TWEEN® 20 were tested against Western plant bug,Lygus hesperus. The percent control determined three days after thetreatment were as shown in table 23.

As shown in table 23, the observed percent control of the pesticidalcomposition against plant bugs (100%) was higher than the expectedpercentage control according to Colby's equation (92%). This was about8.7% improvement over the Colby's expected action. Therefore, thepesticidal composition comprising 0.04 weight % of compound I and about0.0003125 weight % of lambda-cyhalothrin showed synergistic effectagainst plant bug, Lygus hesperus.

TABLE 23 % Control Three Days Treatment for Dose Rate After Plant Bugs,Lygus hesperus (weight %) Treatment Compound I 0.04  0%Lambda-Cyhalothrin 0.0003125 92% Compound I (+) Lambda-Cyhalothrin0.04 + 0.0003125 100%  Observed Action Compound I (+) Lambda-Cyhalothrin0.04 + 0.0003125 92% Colby's Expected Action Compound I (+)Lambda-Cyhalothrin 0.04 + 0.0003125  8% Differences: Observed vs.Expected

Example 15 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I) orN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II) and lambda-Cyhalothrin

A pesticidal composition may be prepared by thoroughly mixing compound I(weight %) or compound II (weight %) with lambda-cyhalothrin (weight %).

The bioassays may be performed for different active compounds againstWestern flower thrips, Frankliniella occidentalis (Pergande), using thesame procedure as that described in example 5. The percent control maybe determined some time after the treatment.

The bioassays may be performed for different active compounds againstCotton Aphid, Aphis gossypii (Glover), using the same procedure as thatdescribed in example 6. The percent control may be determined some timeafter the treatment.

The bioassays may be performed for different active compounds againstBrown Stink Bug, Euschistus Servus (Say), using the same procedure asthat described in example 7. The percent control may be determined sometime after the treatment.

The bioassays may be performed for different active compounds againstLygus bug, Lygus hesperus (Knight), using the same procedure as thatdescribed in example 8. The percent control may be determined some timeafter the treatment.

The bioassays may be performed for different active compounds againstSouth African Brown Stink Bugs, Euschistus heros, using the sameprocedure as that described in example 9. The percent control may bedetermined some time after the treatment.

The bioassays may be performed for different active compounds againstWestern flower thrips, Frankliniella occidentalis, using the sameprocedure as that described in example 13. The percent control may bedetermined some time after the treatment.

The bioassays may be performed for different active compounds againstWestern Plant Bug, Lygus hesperus, using the same procedure as thatdescribed in example 14. The percent control may be determined some timeafter the treatment.

The observed percent control of the pesticidal composition againstWestern flower thrips, Frankliniella occidentalis (Pergande) is expectedto be higher than the expected percentage control according to Colby'sequation. Therefore, the pesticidal composition comprising compound I(weight %) or compound II (weight %) and lambda-cyhalothrin (weight %)is expected to show synergistic effect against Western flower thrips,Frankliniella occidentalis (Pergande).

The observed percent control of the pesticidal composition againstCotton Aphid, Aphis gossypii (Glover) is expected to be higher than theexpected percentage control according to Colby's equation. Therefore,the pesticidal composition comprising compound I (weight %) or compoundII (weight %) and lambda-cyhalothrin (weight %) is expected to showsynergistic effect against Cotton Aphid, Aphis gossypii (Glover).

The observed percent control of the pesticidal composition against BrownStink Bug, Euschistus Servus (Say) is expected to be higher than theexpected percentage control according to Colby's equation. Therefore,the pesticidal composition comprising compound I (weight %) or compoundII (weight %) and lambda-cyhalothrin (weight %) is expected to showsynergistic effect against Cotton Aphid, Aphis gossypii (Glover).

The observed percent control of the pesticidal composition against Lygusbug, Lygus hesperus (Knight) is expected to be higher than the expectedpercentage control according to Colby's equation. Therefore, thepesticidal composition comprising compound I (weight %) or compound II(weight %) and lambda-cyhalothrin (weight %) is expected to showsynergistic effect against Lygus bug, Lygus hesperus (Knight).

The observed percent control of the pesticidal composition against SouthAfrican Brown Stink Bugs, Euschistus heros is expected to be higher thanthe expected percentage control according to Colby's equation.Therefore, the pesticidal composition comprising compound I (weight %)or compound II (weight %) and lambda-cyhalothrin (weight %) is expectedto show synergistic effect against South African Brown Stink Bugs,Euschistus heros.

The observed percent control of the pesticidal composition againstWestern flower thrips, Frankliniella occidentalis is expected to behigher than the expected percentage control according to Colby'sequation. Therefore, the pesticidal composition comprising compound I(weight %) or compound II (weight %) and lambda-cyhalothrin (weight %)is expected to show synergistic effect against Western flower thrips,Frankliniella occidentalis.

The observed percent control of the pesticidal composition againstWestern Plant Bug, Lygus hesperus is expected to be higher than theexpected percentage control according to Colby's equation. Therefore,the pesticidal composition comprising compound I (weight %) or compoundII (weight %) and lambda-cyhalothrin (weight %) is expected to showsynergistic effect against Western Plant Bug, Lygus hesperus.

Example 16 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I) orN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II) and lambda-Cyhalothrin

An emulsifying concentrate pesticidal composition may be prepared bymixing compound I (weight %) or compound II (weight %) withlambda-cyhalothrin (weight %) according to example 10.

The bioassays may be performed for different active compounds againstBrown Stink Bugs, Euschistus servus (Say), using the same procedure asthat described in example 10. The percent control may be determined sometime after the treatment.

The bioassays may be performed for different active compounds againstGreen Stink Bugs, Nezara viridula, using the same procedure as thatdescribed in example 11. The percent control may be determined some timeafter the treatment.

The bioassays may be performed for different active compounds againstStink Bugs, Edessa meditabunda, Euschistus heros, and Piezodorusguildinii, using the same procedure as that described in example 12. Thepercent control may be determined some time after the treatment.

The observed percent control of the pesticidal composition against BrownStink Bugs, Euschistus servus (Say) is expected to be higher than theexpected percentage control according to Colby's equation. Therefore,the pesticidal composition comprising compound I (weight %) or compoundII (weight %) and lambda-cyhalothrin (weight %) is expected to showsynergistic effect against Brown Stink Bugs, Euschistus servus (Say).

The observed percent control of the pesticidal composition against GreenStink Bugs, Nezara viridula, is expected to be higher than the expectedpercentage control according to Colby's equation. Therefore, thepesticidal composition comprising compound I (weight %) or compound II(weight %) and lambda-cyhalothrin (weight %) is expected to showsynergistic effect against Green Stink Bugs, Nezara viridula.

The observed percent control of the pesticidal composition against StinkBugs, Edessa meditabunda, Euschistus heros, and Piezodorus guildinii, isexpected to be higher than the expected percentage control according toColby's equation. Therefore, the pesticidal composition comprisingcompound I (weight %) or compound II (weight %) and lambda-cyhalothrin(weight %) is expected to show synergistic effect against Stink Bugs,Edessa meditabunda, Euschistus heros, and Piezodorus guildinii.

Example 17 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I) and Bifenthrin Against Brown Stink Bug, Euschistus heros Example 17A

Two emulsifying concentrate pesticidal compositions with a weight ratioof compound I to bifenthrin of 1:1 were prepared. The first comprising0.0167 weight % of compound I and about 0.0167 weight % of bifenthrinand the second comprising 0.0333 weight % compound I and 0.0333 weight %bifenthrin. The compositions were diluted and applied to the field usinga spray volume of 150 L/ha. The application was done using a CO₂backpack sprayer with a solid cone nozzle TXVK-8 (ConeJet). Plants wereallowed to air dry and then were placed in a mesh cage where differentinstar stink bugs were infested in two different trials (3^(rd) and4^(th) nymphal stage, and adults). Average stink bug mortality wasassessed at 1, 2, 4, and 7 days after application counting the number ofdead insects and calculating the percent control based on thesurvivorship in the untreated treatment.

The percent control determined 1, 2, 4, and 7 days after the treatmentwere averaged and were as shown in table 24. The average percent controlof the pesticidal composition against brown stink bugs, Euschistusheros, was determined as the “Average Observed” action, and compared tothe average of those obtained by using about 0.0167 weight %, 0.0333weight %, and 0.0667 weight % of compound I alone, and the average ofthose obtained using about 0.0167 weight % and 0.0333 weight % ofbifenthrin alone. The “Colby's Expected Action” was calculated usingColby's equation as discussed previously.

As shown in table 24, the average observed percent control of thepesticidal composition against stink bugs (61.8%) was higher than theexpected percentage control according to Colby's equation (47.0%). Thiswas about 14.8% improvement over the Colby's expected action. Therefore,the pesticidal compositions comprising a weight ratio of 1:1 of compoundI to bifenthrin showed significant synergistic effect against brownstink bugs, Euschistus heros, for the field test.

TABLE 24 Weight Ratio Treatment for of Compound I Average Brown StinkBugs to Bifenthrin % Control Compound I 1:0 9.34% Bifenthrin 0:1 41.6%Compound I (+) Bifenthrin 1:1 61.8% Average Observed Action Compound I(+) Bifenthrin 1:1 47.0% Colby's Expected Action Compound I (+)Bifenthrin 1:1 14.8% Differences: Observed vs. Expected

Example 17B

An emulsifying concentrate pesticidal composition with a weight ratio ofcompound I to bifenthrin of 1:2 were prepared comprising 0.0167 weight %of compound I and about 0.0333 weight % of bifenthrin. The compositionwas diluted and applied to the field using a spray volume of 150 L/ha.The application was done using a CO₂ backpack sprayer with a solid conenozzle TXVK-8 (ConeJet). Plants were allowed to air dry and then wereplaced in a mesh cage where different instar stink bugs were infested intwo different trials (3^(rd) and 4^(th) nymphal stage, and adults).Average stink bug mortality was assessed at 1, 2, 4, and 7 days afterapplication counting the number of dead insects and calculating thepercent control based on the survivorship in the untreated treatment.

The percent control determined 1, 2, 4, and 7 days after the treatmentwere averaged and were as shown in table 25. The average percent controlof the pesticidal composition against brown stink bugs, Euschistusheros, was determined as the “Average Observed” action, and compared tothe average of those obtained by using about 0.0167 weight %, 0.0333weight %, and 0.0667 weight % of compound I alone, and the average ofthose obtained using about 0.0167 weight % and 0.0333 weight % ofbifenthrin alone. The “Colby's Expected Action” was calculated usingColby's equation as discussed previously.

As shown in table 25, the average observed percent control of thepesticidal composition against stink bugs (63.7%) was higher than theexpected percentage control according to Colby's equation (47.0%). Thiswas about 16.7% improvement over the Colby's expected action. Therefore,the pesticidal composition comprising a weight ratio of 1:2 of compoundI to bifenthrin showed significant synergistic effect against brownstink bugs, Euschistus heros, for the field test.

TABLE 25 Weight Ratio Treatment for of Compound I Average Brown StinkBugs to Bifenthrin % Control Compound I 1:0 9.34% Bifenthrin 0:1 41.6%Compound I (+) Bifenthrin 1:2 63.7% Average Observed Action Compound I(+) Bifenthrin 1:2 47.0% Colby's Expected Action Compound I (+)Bifenthrin 1:2 16.7% Differences: Observed vs. Expected

Example 17C

An emulsifying concentrate pesticidal composition with a weight ratio ofcompound I to bifenthrin of 4:1 were prepared comprising 0.0667 weight %of compound I and about 0.0167 weight % of bifenthrin. The compositionwas diluted and applied to the field using a spray volume of 150 L/ha.The application was done using a CO₂ backpack sprayer with a solid conenozzle TXVK-8 (ConeJet). Plants were allowed to air dry and then wereplaced in a mesh cage where different instar stink bugs were infested intwo different trials (3^(rd) and 4^(th) nymphal stage, and adults).Average stink bug mortality was assessed at 1, 2, 4, and 7 days afterapplication counting the number of dead insects and calculating thepercent control based on the survivorship in the untreated treatment.

The percent control determined 1, 2, 4, and 7 days after the treatmentwere averaged and were as shown in table 26. The average percent controlof the pesticidal composition against brown stink bugs, Euschistusheros, was determined as the “Average Observed” action, and compared tothe average of those obtained by using about 0.0167 weight %, 0.0333weight %, and 0.0667 weight % of compound I alone, and the average ofthose obtained using about 0.0167 weight % and 0.0333 weight % ofbifenthrin alone. The “Colby's Expected Action” was calculated usingColby's equation as discussed previously.

As shown in table 26, the average observed percent control of thepesticidal composition against stink bugs (53.6%) was higher than theexpected percentage control according to Colby's equation (47.0%). Thiswas about 6.53% improvement over the Colby's expected action. Therefore,the pesticidal composition comprising a weight ratio of 4:1 of compoundI to bifenthrin showed significant synergistic effect against brownstink bugs, Euschistus heros, for the field test.

TABLE 26 Weight Ratio Treatment for of Compound I Average Brown StinkBugs to Bifenthrin % Control Compound I 1:0 9.34% Bifenthrin 0:1 41.6%Compound I (+) Bifenthrin 4:1 53.6% Average Observed Action Compound I(+) Bifenthrin 4:1 47.0% Colby's Expected Action Compound I (+)Bifenthrin 4:1 6.53% Differences: Observed vs. Expected

Example 18 Synergistic Effect ofN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I) and alpha-Cypermethrin Against Brown Stink Bug, Euschistus herosExample 18A

Two emulsifying concentrate pesticidal compositions with a weight ratioof compound I to alpha-cypermethrin of 1:1 were prepared. The firstcomprising 0.0167 weight % of compound I and about 0.0167 weight % ofalpha-cypermethrin and the second comprising 0.0333 weight % compound Iand 0.0333 weight % alpha-cypermethrin. The compositions were dilutedand applied to the field using a spray volume of 150 L/ha. Theapplication was done using a CO₂ backpack sprayer with a solid conenozzle TXVK-8 (ConeJet). Plants were allowed to air dry and then wereplaced in a mesh cage where different instar stink bugs were infested(3^(rd) and 4^(th) nymphal stage, and adults). Average stink bugmortality was assessed at 1 and 3 days after application counting thenumber of dead insects and calculating the percent control based on thesurvivorship in the untreated.

The percent control determined 1 and 3 days after the treatment wereaveraged and were as shown in table 27. The average percent control ofthe pesticidal composition against brown stink bugs, Euschistus heros,was determined as the “Average Observed” action, and compared to theaverage of those obtained by using about 0.0167 weight %, 0.0333 weight%, and 0.0667 weight % of compound I alone, and the average of thoseobtained using about 0.0167 weight % and 0.0333 weight % ofalpha-cypermethrin alone. The “Colby's Expected Action” was calculatedusing Colby's equation as discussed previously.

As shown in table 27, the average observed percent control of thepesticidal composition against stink bugs (37.5%) was higher than theexpected percentage control according to Colby's equation (26.6%). Thiswas about 10.9% improvement over the Colby's expected action. Therefore,the pesticidal compositions comprising a weight ratio of 1:1 of compoundI to alpha-cypermethrin showed significant synergistic effect againstbrown stink bugs, Euschistus heros, for the field test.

TABLE 27 Weight Ratio of Compound I Treatment for to alpha- AverageBrown Stink Bugs cypermethrin % Control Compound I 1:0 6.93%alpha-Cypermethrin 0:1 21.1% Compound I (+) alpha-Cypermethrin 1:1 37.5%Average Observed Action Compound I (+) alpha-Cypermethrin 1:1 26.6%Colby's Expected Action Compound I (+) alpha-Cypermethrin 1:1 10.9%Differences: Observed vs. Expected

Example 18B

An emulsifying concentrate pesticidal composition with a weight ratio ofcompound I to alpha-cypermethrin of 1:2 were prepared comprising 0.0167weight % of compound I and about 0.0333 weight % of alpha-cypermethrin.The composition was diluted and applied to the field using a sprayvolume of 150 L/ha. The application was done using a CO₂ backpacksprayer with a solid cone nozzle TXVK-8 (ConeJet). Plants were allowedto air dry and then were placed in a mesh cage where different instarstink bugs were infested in two different trials (3^(rd) and 4^(th)nymphal stage, and adults). Average stink bug mortality was assessed at1 and 3 days after application counting the number of dead insects andcalculating the percent control based on the survivorship in theuntreated treatment.

The percent control determined 1 and 3 days after the treatment wereaveraged and were as shown in table 28. The average percent control ofthe pesticidal composition against brown stink bugs, Euschistus heros,was determined as the “Average Observed” action, and compared to theaverage of those obtained by using about 0.0167 weight %, 0.0333 weight%, and 0.0667 weight % of compound I alone, and the average of thoseobtained using about 0.0167 weight % and 0.0333 weight % ofalpha-cypermethrin alone. The “Colby's Expected Action” was calculatedusing Colby's equation as discussed previously.

As shown in table 28, the average observed percent control of thepesticidal composition against stink bugs (33.9%) was higher than theexpected percentage control according to Colby's equation (26.6%). Thiswas about 7.30% improvement over the Colby's expected action. Therefore,the pesticidal composition comprising a weight ratio of 1:2 of compoundI to alpha-cypermethrin showed significant synergistic effect againstbrown stink bugs, Euschistus heros, for the field test.

TABLE 28 Weight Ratio of Compound I Treatment for to alpha- AverageBrown Stink Bugs Cypermethrin % Control Compound I 1:0 6.93%alpha-Cypermethrin 0:1 21.1% Compound I (+) alpha-Cypermethrin 1:2 33.9%Average Observed Action Compound I (+) alpha-Cypermethrin 1:2 26.6%Colby's Expected Action Compound I (+) alpha-Cypermethrin 1:2 7.30%Differences: Observed vs. Expected

Example 18C

Two emulsifying concentrate pesticidal compositions with a weight ratioof compound I to alpha-cypermethrin of 2:1 were prepared. The firstcomprising 0.0333 weight % of compound I and about 0.0167 weight % ofalpha-cypermethrin and the second comprising 0.0667 weight % compound Iand 0.0333 weight % alpha-cypermethrin. The compositions were dilutedand applied to the field using a spray volume of 150 L/ha. Theapplication was done using a CO₂ backpack sprayer with a solid conenozzle TXVK-8 (ConeJet). Plants were allowed to air dry and then wereplaced in a mesh cage where different instar stink bugs were infested(3^(rd) and 4^(th) nymphal stage, and adults). Average stink bugmortality was assessed at 1 and 3 days after application counting thenumber of dead insects and calculating the percent control based on thesurvivorship in the untreated.

The percent control determined 1 and 3 days after the treatment wereaveraged and were as shown in table 29. The average percent control ofthe pesticidal composition against brown stink bugs, Euschistus heros,was determined as the “Average Observed” action, and compared to theaverage of those obtained by using about 0.0167 weight %, 0.0333 weight%, and 0.0667 weight % of compound I alone, and the average of thoseobtained using about 0.0167 weight % and 0.0333 weight % ofalpha-cypermethrin alone. The “Colby's Expected Action” was calculatedusing Colby's equation as discussed previously.

As shown in table 29, the average observed percent control of thepesticidal composition against stink bugs (32.2%) was higher than theexpected percentage control according to Colby's equation (26.6%). Thiswas about 5.63% improvement over the Colby's expected action. Therefore,the pesticidal compositions comprising a weight ratio of 1:1 of compoundI to alpha-cypermethrin showed significant synergistic effect againstbrown stink bugs, Euschistus heros, for the field test.

TABLE 29 Weight Ratio of Compound I Treatment for to alpha- AverageBrown Stink Bugs Cypermethrin % Control Compound I 1:0 6.93%alpha-Cypermethrin 0:1 21.1% Compound I (+) alpha-Cypermethrin 2:1 32.2%Average Observed Action Compound I (+) alpha-Cypermethrin 2:1 26.6%Colby's Expected Action Compound I (+) alpha-Cypermethrin 2:1 5.63%Differences: Observed vs. Expected

Example 18D

An emulsifying concentrate pesticidal composition with a weight ratio ofcompound I to alpha-cypermethrin of 4:1 were prepared comprising 0.0667weight % of compound I and about 0.0167 weight % of alpha-cypermethrin.The composition was diluted and applied to the field using a sprayvolume of 150 L/ha. The application was done using a CO₂ backpacksprayer with a solid cone nozzle TXVK-8 (ConeJet). Plants were allowedto air dry and then were placed in a mesh cage where different instarstink bugs were infested in two different trials (3^(rd) and 4^(th)nymphal stage, and adults). Average stink bug mortality was assessed at1 and 3 days after application counting the number of dead insects andcalculating the percent control based on the survivorship in theuntreated treatment.

The percent control determined 1 and 3 days after the treatment wereaveraged and were as shown in table 30. The average percent control ofthe pesticidal composition against brown stink bugs, Euschistus heros,was determined as the “Average Observed” action, and compared to theaverage of those obtained by using about 0.0167 weight %, 0.0333 weight%, and 0.0667 weight % of compound I alone, and the average of thoseobtained using about 0.0167 weight % and 0.0333 weight % ofalpha-cypermethrin alone. The “Colby's Expected Action” was calculatedusing Colby's equation as discussed previously.

TABLE 30 Weight Ratio of Compound I Treatment for to alpha- AverageBrown Stink Bugs Cypermethrin % Control Compound I 1:0 6.93%alpha-Cypermethrin 0:1 21.1% Compound I (+) alpha-Cypermethrin 4:1 19.2%Average Observed Action Compound I (+) alpha-Cypermethrin 4:1 26.6%Colby's Expected Action Compound I (+) alpha-Cypermethrin 4:1 −7.35% Differences: Observed vs. Expected

While the present disclosure may be susceptible to various modificationsand alternative forms, specific embodiments have been described by wayof example in detail herein. However, it should be understood that thepresent disclosure is not intended to be limited to the particular formsdisclosed. Rather, the present disclosure is to cover all modifications,equivalents, and alternatives falling within the scope of the presentdisclosure as defined by the following appended claims and their legalequivalents.

We claim:
 1. A pesticidal composition comprising a synergisticallyeffective amount of: a pyrethroid-based or pyrethrin-based sodiumchannel modulator compound; and a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.


2. The composition of claim 1, wherein the pyrethroid-based orpyrethrin-based sodium channel modulator compound comprises at least oneof lambda-cyhalothrin, acrinathrin, allethrin, d-cis-trans allethrin,d-trans allethrin, bifenthrin, bioallethrin, bioallethrinS-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin,beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, cypermethrin,alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin,zeta-cypermethrin, cyphenothrin [(1R)-trans-isomers], deltamethrin,empenthrin [(EZ)-(1R)-isomers], esfenvalerate, etofenprox,fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate,halfenprox, imiprothrin, kadethrin, permethrin, phenothrin[(1R)-trans-isomer], prallethrin, pyrethrins (pyrethrum), resmethrin,silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R)-isomers],tralomethrin, and transfluthrin.
 3. The composition of claim 1, whereinthe pyrethroid-based or pyrethrin-based sodium channel modulatorcompound comprises lambda-cyhalothrin.
 4. The composition of claim 1,further comprising a phytologically-acceptable inert carrier.
 5. Thecomposition of claim 1, further comprising an additive selected from asurfactant, a stabilizer, an emetic agent, a disintegrating agent, anantifoaming agent, a wetting agent, a dispersing agent, a binding agent,dye, filler, or combinations thereof.
 6. The composition of claim 1,further comprising one or more compounds having acaricidal, algicidal,avicidal, bactericidal, fungicidal, herbicidal, insecticidal,molluscicidal, nematicidal, rodenticidal, virucidal or combinationsthereof properties.
 7. The composition of claim 1, further comprisingone or more compounds that are antifeedants, bird repellents,chemosterilants, herbicide safeners, insect attractants, insectrepellents, mammal repellents, mating disrupters, plant activators,plant growth regulators, synergists, or combinations thereof.
 8. Thecomposition of claim 1, wherein a weight ratio of the pesticide selectedfrom (I), (II) or any agriculturally acceptable salt thereof to thepyrethroid-based or pyrethrin-based sodium channel modulator compound isno more than about 2000:1.
 9. The composition of claim 1, wherein aweight ratio of the pesticide selected from (I), (II) or anyagriculturally acceptable salt thereof to the pyrethroid-based orpyrethrin-based sodium channel modulator compound is no more than about513:1.
 10. The composition of claim 1, wherein a weight ratio of thepesticide selected from (I), (II) or any agriculturally acceptable saltthereof to the pyrethroid-based or pyrethrin-based sodium channelmodulator compound is no more than about 256:1.
 11. The composition ofclaim 1, wherein a weight ratio of the pesticide selected from (I), (II)or any agriculturally acceptable salt thereof to the pyrethroid-based orpyrethrin-based sodium channel modulator compound is no more than about128:1.
 12. The composition of claim 1, wherein a weight ratio of thepesticide selected from (I), (II) or any agriculturally acceptable saltthereof to the pyrethroid-based or pyrethrin-based sodium channelmodulator compound is no more than about 32:1.
 13. The composition ofclaim 1, wherein a weight ratio of the pesticide selected from (I), (II)or any agriculturally acceptable salt thereof to the pyrethroid-based orpyrethrin-based sodium channel modulator compound is no more than about16:1.
 14. The composition of claim 1, wherein a weight ratio of thepesticide selected from (I), (II) or any agriculturally acceptable saltthereof to the pyrethroid-based or pyrethrin-based sodium channelmodulator compound is no more than about 8:1.
 15. The composition ofclaim 1, wherein a weight ratio of the pesticide selected from (I), (II)or any agriculturally acceptable salt thereof to the pyrethroid-based orpyrethrin-based sodium channel modulator compound is no more than about7.5:1.
 16. The composition of claim 1, wherein a weight ratio of thepesticide selected from (I), (II) or any agriculturally acceptable saltthereof to the pyrethroid-based or pyrethrin-based sodium channelmodulator compound is no more than about 5:1.
 17. The composition ofclaim 1, wherein a weight ratio of the pesticide selected from (I), (II)or any agriculturally acceptable salt thereof to the pyrethroid-based orpyrethrin-based sodium channel modulator compound is no more than about4:1.
 18. The composition of claim 1, wherein a weight ratio of thepesticide selected from (I), (II) or any agriculturally acceptable saltthereof to the pyrethroid-based or pyrethrin-based sodium channelmodulator compound is no more than about 3.8:1.
 19. The composition ofclaim 1, wherein a weight ratio of the pesticide selected from (I), (II)or any agriculturally acceptable salt thereof to the pyrethroid-based orpyrethrin-based sodium channel modulator compound is no more than about2.5:1.
 20. The composition of claim 1, wherein a weight ratio of thepesticide selected from (I), (II) or any agriculturally acceptable saltthereof to the pyrethroid-based or pyrethrin-based sodium channelmodulator compound is no more than about 2:1.
 21. The composition ofclaim 1, wherein a weight ratio of the pesticide selected from (I), (II)or any agriculturally acceptable salt thereof to the pyrethroid-based orpyrethrin-based sodium channel modulator compound is no more than about1.7:1.
 22. The composition of claim 1, wherein a weight ratio of thepesticide selected from (I), (II) or any agriculturally acceptable saltthereof to the pyrethroid-based or pyrethrin-based sodium channelmodulator compound is no more than about 1:2.5.
 23. The composition ofclaim 1, wherein a weight ratio of the pesticide selected from (I), (II)or any agriculturally acceptable salt thereof to the pyrethroid-based orpyrethrin-based sodium channel modulator compound is no more than about1:1.
 24. The composition of claim 1, wherein the weight ratio of thepesticide (I), (II), or any agriculturally acceptable salt thereof andthe pyrethroid-based or pyrethrin-based sodium channel modulatorcompound is X:Y; wherein, X is the parts by weight of the pesticide (I),(II), or any agriculturally acceptable salt thereof, and the numericalrange is 0<X≦20; Y is the parts by weight of the pyrethroid-based orpyrethrin-based sodium channel modulator compound, and the numericalrange is 0<Y≦20.
 25. The composition of claim 24, wherein the ranges ofweight ratios of the pesticide (I), (II), or any agriculturallyacceptable salt thereof and the pyrethroid-based or pyrethrin-basedsodium channel modulator compound are X₁:Y₁ to X₂:Y₂, wherein one of thefollowing conditions is satisfied: (a) X₁>Y₁ and X₂<Y₂; or (b) X₁>Y₁ andX₂>Y₂; or (c) X₁<Y₁ and X₂<Y₂.
 26. A method of controlling pestscomprising applying a pesticidal composition near a population of pests,wherein the pesticidal composition comprises a synergistically effectiveamount of: a pyrethroid-based or pyrethrin-based sodium channelmodulator compound; and a pesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.


27. The method of claim 26, wherein the pyrethroid-based orpyrethrin-based sodium channel modulator compound comprises at least oneof lambda-cyhalothrin, acrinathrin, allethrin, d-cis-trans allethrin,d-trans allethrin, bifenthrin, bioallethrin, bioallethrinS-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin,beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, cypermethrin,alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin,zeta-cypermethrin, cyphenothrin [(1R)-trans-isomers], deltamethrin,empenthrin [(EZ)-(1R)-isomers], esfenvalerate, etofenprox,fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate,halfenprox, imiprothrin, kadethrin, permethrin, phenothrin[(1R)-trans-isomer], prallethrin, pyrethrins (pyrethrum), resmethrin,silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R)-isomers],tralomethrin, and transfluthrin.
 28. The method of claim 26, wherein thepyrethroid-based or pyrethrin-based sodium channel modulator compoundcomprises lambda-cyhalothrin.
 29. The method of claim 26, wherein thepyrethroid-based or pyrethrin-based sodium channel modulator compoundcomprises bifenthrin.
 30. The method of claim 26, wherein thepyrethroid-based or pyrethrin-based sodium channel modulator compoundcomprises alpha-cypermethrin.
 31. The method of claim 26, wherein thepests are sucking insects, chewing insects, or a combination thereof.32. The method of claim 26, wherein the pests comprise at least one ofWestern flower thrips, Frankliniella occidentalis (Pergande), cottonaphid, Aphis gossypii (Glover), brown stink bug, Euschistus heros,Euschistus serous (Say) and Lygus bug, Lygus hesperus (Knight).
 33. Amethod for protecting a plant from infestation and attack by pests, themethod comprising: contacting the plant with a pesticidal compositioncomprising a synergistically effective amount of a pyrethroid-based orpyrethrin-based sodium channel modulator compound in combination with apesticide selected fromN-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)thio)propanamide(I),N-(3-chloro-1-(pyridin-3-yl)-1H-pyrazol-4-yl)-N-ethyl-3-((3,3,3-trifluoropropyl)sulfinyl)propanamide(II), or any agriculturally acceptable salt thereof.


34. The method of claim 33, wherein the pyrethroid-based orpyrethrin-based sodium channel modulator compound comprises at least oneof lambda-cyhalothrin, acrinathrin, allethrin, d-cis-trans allethrin,d-trans allethrin, bifenthrin, bioallethrin, bioallethrinS-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin,beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, cypermethrin,alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin,zeta-cypermethrin, cyphenothrin [(1R)-trans-isomers], deltamethrin,empenthrin [(EZ)-(1R)-isomers], esfenvalerate, etofenprox,fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate,halfenprox, imiprothrin, kadethrin, permethrin, phenothrin[(1R)-trans-isomer], prallethrin, pyrethrins (pyrethrum), resmethrin,silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R)-isomers],tralomethrin, and transfluthrin.
 35. The method of claim 33, wherein thepyrethroid-based or pyrethrin-based sodium channel modulator compoundcomprises lambda-cyhalothrin.